Post on 02-Feb-2023
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February 26, 2010
Prediction of SAMPL2 Aqueous Solvation Free Energies and
Tautomeric Ratios Using the SM8, SM8AD, and SMD Solvation Models
Raphael F. Ribeiro, Aleksandr V. Marenich, Christopher J. Cramer,* and Donald G. Truhlar*Department of Chemistry and Supercomputing Institute,
University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455-0431
Abstract: We applied the solvation models SM8, SM8AD, and SMD in combination with the
Minnesota M06-2X density functional to predict vacuum-water transfer free energies (Task 1)
and tautomeric ratios in aqueous solution (Task 2) for the SAMPL2 test set. The bulk-
electrostatic contribution to the free energy of solvation is treated as follows: SM8 employs the
generalized Born model with the Coulomb field approximation, SM8AD employs the
generalized Born approximation with asymmetric descreening, and SMD solves the
nonhomogeneous Poisson equation. The non-bulk-electrostatic contribution arising from short-
range interactions between the solute and solvent molecules in the first solvation shell is treated
as a sum of terms that are products of geometry-dependent atomic surface tensions and solvent-
accessible surface areas of the individual atoms of the solute. On average, three models tested in
the present work perform similarly. In particular, we achieved mean unsigned errors of 1.4
(SM8), 2.0 (SM8AD), and 2.6 kcal/mol (SMD) for the aqueous free energies of 30 out of 31
compounds with known reference data involved in Task 1 and mean unsigned errors of 2.7
(SM8), 1.8 (SM8AD), and 2.4 kcal/mol (SMD) in the free energy differences (tautomeric ratios)
for 21 tautomeric pairs in aqueous solution involved in Task 2.
Keywords: Free energy; Generalized Born; Implicit Solvation; Poisson Equation; Solvation;
Solvation Modeling; Tautomerism
* Corresponding author e-mail: cramer@umn.edu (C.J.C) and truhlar@umn.edu (D.G.T.)
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Introduction
The annual SAMPL challenges organized by OpenEye Scientific Software present the
unique opportunity to make an assessment of various solvation protocols with respect to the
prediction of solvation effects for very diverse solutes including many containing functionality of
interest to the pharmaceutical industry. Accurate theoretical description of solvation is critically
important in modeling because solvation effects are essential components of all liquid-state
chemistry, and it is impossible to understand liquid-phase organic, biological, or inorganic
chemistry without including them. For example, solvation effects influence solvent-dependent
changes in reaction rates and reaction mechanisms, chromatographic retention behavior,
interfacial transport effects, protein folding, ligand-receptor binding, and pharmaceutical
bioavailability. Various explicit and implicit solvation models have been employed for prediction
of pharmacokinetic and thermodynamic properties of drug-like compounds in biological fluids,
for instance, in the evaluation of protein-ligand binding free energies using the free energy of
solvation (or desolvation) of the ligand as a key component [1, 2]. In addition, accurate
computational methods used in solvation modeling may be a viable alternative to experimental
measurement, especially for highly polar solutes for which experimental determinations of
solvation free energies are difficult or inaccurate. Solvation models differ in their representation
of the solvent, their adoption of a classical or quantum description of the solute, and their
computational cost [3–10]. As a consequence, their accuracy for the prediction of free energies
of solvation and their range of applicability are also different. The SAMPL initiative is especially
useful because it allows for evaluation of current solvation methods in terms of their predictive
abilities on mostly unpublished and obscure data sets that are unlikely to have been part of the
training set of any tested protocol. The testing of different models against common test sets is a
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particularly valuable exercise that facilitates comparison of their relative strengths and
weaknesses. The insight that one can gain with such an exercise will serve well for further
improvement of existing solvation models and liquid-phase simulation techniques.
The present SAMPL2 challenge is focused on the prediction of vacuum-water transfer
energies (Task 1) and the prediction of tautomer ratios (Task 2) for compounds in solution, many
of which have been selected to be pharmaceutically relevant. The SAMPL2 data set includes
compounds from three different categories: obscure, explanatory, and investigatory. Obscure
compounds have known but not readily available experimental data. Explanatory compounds,
which have unexpected or interesting experimental values, have been included in hopes that the
solvation models involved in the SAMPL2 challenge might explain their unusual properties.
Measured solvation free energies are not available for investigatory compounds. In the present
paper, we evaluate the performance of our most recent implicit solvation models, namely, SM8,
SM8AD, and SMD, over the SAMPL2 test set. Section 2 places the solvation models used in the
present study in the context of recent advances in the field. Section 3 summarizes further
computational details. Section 4 presents results and discussion. Section 5 summarizes our
conclusions.
Review of computational methods
Computational methods that include the solvent implicitly have been recognized as a
powerful alternative to explicit simulation techniques because they allow one to treat the solute
with quantum mechanical calculations at the same high levels as those used in the gas phase [5–
10]. Reliable calculations of solutes in solution must take account of electrostatics, cavitation,
dispersion, and solvent structure. In the most complete implicit solvation models, the solute is
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polarized self-consistently by the reaction field, and it is the interaction of the mutually polarized
solute and solvent subsystems that is called the electrostatic contribution. The electrostatic
contribution can be evaluated by solving the Poisson equation for a nonhomogeneous dielectric
medium with the free charge being that of the continuous charge density of the solute or by using
alternative approaches, for instance, the generalized Born (GB) approximation [11–13], which
represents the solute as a system of point charges located at the nuclear positions.
We have recently introduced three successively improved self-consistent reaction-field
continuum solvation models, namely Solvation Model 8 (SM8) [14], Solvation Model 8 with
Asymmetric Descreening (SM8AD) [15], and Solvation Model D (SMD) [16]. “Continuum”
denotes that the solvent is not represented explicitly in any of these models, but rather it is
treated as a dielectric medium with variable surface tension at the solute-solvent boundary. These
models separate the observable solvation free energy into three components. One of
these, depends on solute concentration and vanishes for an ideal solution with the same
concentration as the vapor. The other two are independent of concentration and correspond to a
dilute solution. Thus the standard-state free energy of solvation is
,Δ οconcG
CDSENPconcS GGG ++= GΔΔΔ οo (1)
where ΔGENP is the bulk electrostatic contribution resulting from the interaction of a solute with
its reaction field, which is the electric field produced by the polarized charge density that the
solute induces in the solvent, and GCDS is explained below. The solute cavity for the bulk
electrostatic calculation is taken as a superposition of nuclear-centered spheres, and the solvent
dielectric constant is taken as its bulk value right up to cavity boundary. The final component in
Eq. 1 accounts for everything except concentration and that part of the electrostatic contribution
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that is modeled with the bulk dielectric constant. It is nominally associated with cavity
formation, dispersion, and solvent-structure effects, but it also includes the deviation from the
assumed bulk behavior of the solute electrostatic interaction with the first solvent shell. Since the
third contribution is semiempirical it also makes up for any systematic errors such as the inexact
treatment of solutes. The third contribution will be called the CDS term, denoting the nominal
ingredients of cavitation, dispersion, and solvent structure. All the three models are used in the
present study in their standard, published form, with no changes for the present applications.
The bulk electrostatic contribution is treated differently in SM8, SM8AD, and SMD. The
SMD model is based on the polarized continuous quantum mechanical charge density of the
solute (the “D” in the name stands for “density”). The SMD bulk electrostatic contribution to the
free energy of solvation arises from a self-consistent reaction field treatment that involves
solution of the nonhomogeneous Poisson equation (NPE) by the Integral-Equation-Formalism
Polarizable Continuum Model (IEF-PCM) algorithm [17]. In contrast to SMD, the SM8 and
SM8AD models treat the bulk electrostatics using the GB approximation based on partial atomic
charges, whose interaction with the solvent and with each other is dielectrically screened by the
polarized solvent and descreened by other parts of the solute. The SM8 and SM8AD models treat
dielectric descreening effects in terms of the so-called Born radii of individual atoms in the
solute molecule. The SM8 model employs the Born radius based on the Coulomb field
approximation of Still et al. [13]. The SM8AD model improves on the earlier SM8 model by
using a new asymmetric descreening algorithm with a modified formula for the Born radius
suggested by Grycuk [18]. Both the SM8 and SM8AD models employ class IV charge models
[19], in particular, Charge Model 4 (CM4) [20] and Charge Model 4M (CM4M) [21]. In the
present work we use only CM4M.
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The CDS contribution to the free energy of solvation computed by SM8, SM8AD, and
SMD is a sum of terms that are proportional (with geometry-dependent proportionality constants
called atomic surface tensions) to the solvent-accessible surface areas of the individual atoms of
the solute. The CDS terms were parameterized [14–16] to include all of the deviations of the
electrostatics from the assumed bulk model, such as the inexactness of the solvent permittivity
model, including assumed values for intrinsic Coulomb radii, uncertainties in the treatment of
solute charge outside the solute cavity in the case of SMD, and the inexactness of the solute
charge model in the case of SM8 and SM8AD.
The SM8, SM8AD, and SMD models have been recently tested using 26 combinations of
various basis sets and density functionals over a set of 2892 solvation data including 345 free
energies of solvation for neutral solutes in water, 2072 free energies of solvation for neutral
solutes in 90 nonaqueous solvents, 143 transfer free energies for neutral solutes between water
and 15 organic solvents, and 332 free energies of solvation for ions in acetonitrile, dimethyl
sulfoxide, methanol, and water [15]. The number of solvation energy calculations performed in
this testing totals 75192 for each of the three models. The mean unsigned error averaged over 26
theoretical levels for 2560 solvation data for neutral solutes is 0.6, 0.7, and 0.8 kcal/mol for
SM8AD, SM8, and SMD, respectively. The mean unsigned error averaged over 26 theoretical
levels for 332 free energies of solvation for ions is 4.0 (SM8AD), 4.4 (SM8), and 4.3 kcal/mol
(SMD). Although all the three models perform nearly equally well, one should consider that the
SM8 and SM8AD models employ partial atomic charges, and their accuracy for a particular level
of electronic structure theory may depend on whether consistent partial charges can be computed
for that level of theory, but the ability to compute such partial atomic charges is not guaranteed
for all possible theory levels and basis sets. For this reason, solvation models that solve the NPE
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such as the density-based model SMD are deemed to be less sensitive to the choice of basis set,
although basis sets containing diffuse functions can lead to errors due to charge lying outside the
solute cavity [22]. On the other hand, the GB models such as SM8 and SM8AD can be favored
for their lower computational cost compared to the cost of NPE solvers; one SCF iteration
typically takes 1.5 – 2 times longer with SMD than with SM8 or SM8AD. Comparing the two
GB approaches, we note that the SM8AD model based on the asymmetric descreening
approximation [15, 18] is expected to be more realistic than the SM8 model, which is based on
the Coulomb field approximation of Still et al. [13], particularly for cases when the individual
partial atomic charges are asymmetrically situated in the molecule, i.e., located near the
dielectric boundary rather than at the center of the molecular surface [15, 18].
Computational details
All the solvation free energies are given for the gas-phase solute having a standard state
of an ideal gas at a gas-phase concentration of 1 mol/L and for the liquid-phase solute being
dissolved in an ideal solution at a liquid-phase concentration of 1 mol/L, and the temperature is
298 K. In this case in Eq. 1 becomes Free energies that employ this standard
state definition will be denoted by the superscript “*”. When one uses the same geometry in the
gas phase and in solution (as we do here), ΔGENP reduces to ΔGEP.
οΔ concG .0Δ ο ≡concG
Following our earlier work on the SAMPL1 challenge [23] all free energies of solvation
calculated for Task 1 (Transfer Energies) were computed using the Minnesota solvation models
outlined above with the density functional M06-2X [24], and the 6-31G(d) [25, 26] basis set. We
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used the geometries included in the instructions for SAMPL2, except (as discussed below) for
glycerol.
In order to gather further insights into our results, we also computed the free energy of
solvation for the molecules present in the explanatory subset using solvent-solute clusters
composed of the solute and one or two water molecules in chemically intuitive positions, i.e.,
interacting via hydrogen bonding or dipole-dipole forces. Gas-phase structures of the water-
solute clusters were optimized using M06-2X [24]/MG3S [27].
For the solvent-solute clusters with a single water molecule, the free energy of solvation
of a given solute is evaluated using the corresponding thermochemical cycle that relates
to the calculated free energy of solvation of the water-solute cluster, as
follows
(M)S*ΔG
(M)S*ΔG M),O(H2S ⋅*ΔG
]ln[ΔΔΔΔΔ **ο* OHO)(HM)O(H(B.E.) (M) 22S2S*o
gS RTGG −−⋅+−= → GGG (2)
In Eq. 2, is the computed gas-phase binding free energy of the solute-water cluster
that corresponds to the ideal-gas standard state of 1 atm denoted by the superscript “o”,
refers to the free energy change between one mole of an ideal gas taken at
1 atm (24.46 mol/L) and one mole taken at the concentration of 1 mol/L, is the
experimental free energy of solvation of water, and
(B.E.)gοΔG
)46.24ln(Δ RTG ≡→*o
O)(H2S*ΔG
)34.55ln(]ln[ RTRT ≡OH2 refers to the free
energy change between one mole of H2O ideal gas taken at the concentration of H2O in liquid
water (55.34 mol/L) and one mole taken at the concentration of 1 mol/L [16, 28]. A procedure
for calculation of using the solvent-solute clusters with more than one solvent molecules
is described elsewhere [
(M)S*ΔG
28].
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Task 2 (Tautomeric Teasers) involved the calculation of the free energy difference
between two tautomeric forms in solution. The free energy of each tautomer in solution is
calculated as a sum of the corresponding gas-phase free energy and the aqueous free energy of
solvation for a given tautomer. For all the compounds involved in Task 2, the gas-phase free
energies at 298 K were calculated at the M06-2X/MG3S level of theory using the gas-phase
molecular geometries optimized at the same level. The corresponding aqueous free energies of
solvation were computed at the M06-2X/6-31G(d) level of theory at the M06-2X/MG3S gas-
phase geometries using the SM8, SM8AD, and SMD continuum solvation models. To examine
the accuracy of the M06-2X gas-phase free energies, we compared them with those calculated
using the BMC-CCSD multicoefficient correlation method [29] for selected cases in Task 2. In
these computations noted further as BMC-CCSD//M06-2X/MG3S we used the BMC-CCSD total
electronic energies calculated at the M06-2X/MG3S gas-phase geometries with the 298 K
thermal free energy corrections calculated at the M06-2X/MG3S level.
All calculations in this work were performed using two locally modified versions of the
Gaussian03 [30] electronic structure package, namely, Minnesota Gaussian Functional Module
(MN-GFM) [31] and Minnesota Gaussian Solvation Module (MN-GSM) [32].
Results and discussion
Task 1: aqueous free energies of solvation
Task 1 involved the prediction of aqueous free energies of solvation (air-water transfer
energies) for 41 polyfunctional molecules selected by Guthrie (see introduction to SAMPL2
challenge in this issue of the journal) and divided into three groups: a) obscure compounds, b)
explanatory compounds, and c) investigatory compounds. With respect to the explanatory
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compounds, the corresponding experimental aqueous free energies of solvation were provided in
advance, so that unusual trends in the relevant properties of these compounds could be
reproduced and explained. There were no experimental data provided for the investigatory group,
and to the best of our knowledge, there are no experimental solvation energies available for these
compounds in the literature.
TABLE 1
Table 1 compares aqueous free energies of solvation calculated by SM8, SM8AD, and
SMD for 30 out of 31 compounds originally present in the obscure and explanatory subsets to the
corresponding experimental values. Note that we excluded 1-iodouracil from consideration here
because the tested solvation models were not parameterized for iodine-containing compounds.
The biggest outlier among the obscure compounds is diflunisal. Apart from diflunisal, the
accuracy of SM8, SM8AD, and SMD depends on the nature of a tested compound. For example,
SM8AD gives an error of 5.6 kcal/mol for ketoprofen whereas SM8 and SMD show much
smaller deviations of 1.8 (SM8) and 2.1 kcal/mol (SMD), respectively, for the same compound.
In addition, SM8AD overestimates the aqueous free energy of solvation of acetylsalicylic acid by
4.1 kcal/mol whereas the error for SM8 and SMD is only –1.6 kcal/mol on average. SM8AD is
more accurate than SMD and SM8 in the case of sulfolane apparently due to a better
representation of compounds with oxidized sulfur functionalities in the SM8AD training set [15].
In the case of D-xylose and D-glucose, the SMD model is less accurate than SM8 and
SM8AD. However, caution should be exercised before consideration of the experimental data
given in the SAMPL2 database for these carbohydrates because the experimental procedures for
estimating the free energies of solvation of highly polar molecules are prone to a variety of
problems, such as the decomposition of the solute at the high temperatures needed to achieve a
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reasonable vapor pressure, and inherent numerical errors in the extrapolation of the high-
temperature results to the corresponding room-temperature values. On the other hand, the
substantially more negative solvation free energies predicted for the two sugars by SMD may
reflect enhanced outlying charge errors in these molecules heavily functionalized with oxygen
lone pairs near the cavity boundary. Overall, for the set of obscure compounds, SM8 is slightly
more accurate (within the uncertainty of the experimental data) than SM8AD and SMD, with
50% of its predictions giving errors of 1 kcal/mol or less, and only four molecules having errors
greater than 2 kcal/mol.
Table 1 indicates that over the set of explanatory compounds all of our models did poorly
in predicting the experimental solvation free energy of glycerol, with errors ranging from 4 to 8
kcal/mol when we used the geometry of glycerol as provided by OpenEye Scientific Software
without any further structural optimization (and thus with only one conformation of glycerol
being taken into account; see footnote b in Table 1). To further investigate the problem with
glycerol, we performed a conformational search for the global minimum of glycerol using the
MMFF94 [33] force field with the GMMX algorithm present in the PCModel software [34], and
then we re-optimized the two lowest energy conformers at the mPW1PW [35]/MIDI! [36] level.
The aqueous free energies of solvation for the two conformations were calculated using the SM8,
SM8AD, and SMD solvation models. The lowest energy conformer is preferred over the next
higher one by 3.5 kcal/mol in the gas phase and 2.9 kcal/mol in solution (complete details of
solvation free energies with SM8, SM8AD, and SMD are included in the Electronic
Supplementary Material along with the Cartesian coordinates for both glycerol structures). The
resulting SM8, SM8AD, and SMD aqueous solvation free energies calculated for the lowest
conformer in solution are reported in Table 1. These values are in much better agreement with
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experiment (the average deviation is 1.6 kcal/mol) than those calculated using the SAMPL2
original geometry for glycerol (the average deviation is 5.8 kcal/mol). Over all the explanatory
set, SM8 is more accurate than SM8AD and SMD for predicting the aqueous free energy of
solvation of 3 out of the 8 molecules in this group with the accuracy of 1 kcal/mol or less
whereas SM8AD and SMD show such an accuracy for only two molecules of the given subset.
Table 1 also shows mean signed and mean unsigned errors (MSE and MUE, respectively)
as well as root mean squared errors (RMSE) in the predicted energies with respect to experiment.
We conclude that all our models perform reasonably well on either obscure or explanatory set of
compounds in the SAMPL2 challenge, with the MUE ranging from 1.4 kcal/mol (SM8) to 2.6
kcal/mol (SMD) on average.
TABLE 2
Table 2 shows the SM8, SM8AD, and SMD results for the investigatory compounds, for
which no experimental data were given. The investigatory group may be subdivided into three
classes: (i) phosphorous oxidized compounds, (ii) sulfur oxidized compounds, and (iii) azoles.
For the 25 organophosphorus compounds tested in previous work [15], the mean unsigned errors
(relative to the corresponding experimental data) in the SM8, SM8AD, and SMD aqueous free
energies of solvation calculated at the M06-2X/6-31G(d) level of electronic structure theory were
equal to 1.5 (SM8) , 1.3 (SM8AD), and 1.7 kcal/mol (SMD) [15]. These errors are comparable
with the absolute deviations in the SM8, SM8AD, and SMD predictions on
hexamethylphosphoramide, dimethyl methylphosphonate, and methyl dimethylphosphinate,
which are between 0.3 and 3 kcal/mol (Table 2). The mean signed errors in the aqueous free
energies of solvation calculated by SM8, SM8AD, and SMD for the five sulfonylureas tested in
previous work [15] were equal to –10.8 (SM8), –5.5 (SM8AD), and –7.4 kcal/mol (SMD) [15].
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These compounds contain the S–O functionality; therefore, they structurally resemble the
sulfones and sulfoxides presented in Table 3. Thus, for the four sulfones and sulfoxides from the
investigatory set, the SM8AD model should provide the most accurate predictions whereas the
SM8 model (along with SMD for two cases out of four) is likely to overestimate the
corresponding solvation free energies. For oxazole, thiazole, and isothiazole, the absolute
deviations in the corresponding solvation free energies predicted by any two of SM8, SM8AD,
and SMD are between 0.1 and 2 kcal/mol. These deviations are comparable with those obtained
in previous work [15] for imidazole (0.3 – 1.5 kcal/mol) using SM8, SM8AD, and SMD with
M06-2X and 6-31G(d).
Sometimes adding one or more solvent molecules to the solute molecule explicitly can
substantially improve the performance of implicit solvation models [37, 38]. We have examined
such an approach in the present work by clustering all of the molecules in the explanatory
SAMPL2 test set, except glycerol. We added one water molecule to each tested solute molecule
except 4-nitroaniline, for which we added two explicit water molecules. The resulting molecular
structures of the water-solute clusters are presented in Figure 1. Table 3 shows SM8, SM8AD,
and SMD aqueous free energies of solvation of unclustered solutes calculated by Eq. 1 with the
use of the corresponding solvation free energies of the clusters.
FIGURE 1
TABLE 3
In general, the use of explicit solvent molecules for calculation of the solvation free
energy (microsolvation) should improve on only using CDS terms to account for such effects as
charge transfer between the solute molecule and the first solvation shell and the partial covalent
character of strong hydrogen bonds. Table 3 indicates that on average the use of water-solute
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clusters has little effect on the performance of SM8, degrades the performance of SM8AD, and
improves the performance of SMD. When the continuum approximation is justified, that is, when
no “special” first-shell interactions mandate the inclusion of specific first-shell solvent
molecules, the inclusion of one or more explicit solvent molecules should not degrade the
performance of a continuum model (except for the issue that when includes explicit solvent
molecules, one should average properly, in a free energy sense, over their locations, but this is
not done here), and this is the case for SM8. In the SMD model, improvement is observed after
clustering, but derives almost entirely from the two chlorocarbons, suggesting that the atomic
surface tension for Cl may be somewhat too hydrophobic in SMD (so that burying some of the
exposed Cl surface with a clustering solvent molecule leads to an improved solution free
energy). The reason for the poor effect of clustering on the predicted SM8AD solvation free
energies is not clear, but it should be kept in mind that experimental uncertainties are high here.
Task 2: tautomeric teasers
The prediction of tautomeric equilibria presents a number of challenges from a modeling
standpoint. For example many of the tautomeric forms explicitly provided as part of the
challenge can themselves exist in multiple rotameric forms, and to complicate matters further the
lowest-energy rotamer of a given tautomer may be different in the gas phase than in aqueous
solution. In addition, the proximity of multiple hydrophilic functional groups in several of the
tautomers suggests that consideration of explicit first-shell water molecules may be important in
certain instances. A careful consideration of all of these issues, together with proper statistical
averaging over equilibrium populations, should be done in order to make meaningful
comparisons to experiment. Unfortunately, such careful attention devoted to each of the many
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tautomeric equilibria included in this challenge was not possible within the time frame of the
exercise; instead, we elected to begin from the molecular structures provided by the SAMPL2
organizers and not to consider any others. This allows for a comparison of the results from the
SM8, SM8AD, and SMD models to those from solvation models surveyed by other groups as
part of this overall effort, but suggests that it may be dangerous to go beyond such internal
comparison to consider additionally the experimental situation. Certainly we think that it will be
worthwhile to return to many of these tautomeric equilibria in the future and explore all relevant
conformational and methodological issues in detail, but the results presented below should be
recognized as having restricted value beyond method-to-method comparison.
Task 2 involves the prediction of the free energy difference between two tautomers in
aqueous media for twelve cases selected by Taylor and divided into three categories: a) obscure,
b) explanatory, and c) investigatory subsets. The obscure subset comprises cases 1 – 3, the
explanatory subset comprises cases 4 – 6, the investigatory subset comprises cases 7 – 12. The
experimental values for the explanatory compounds are given along with the SAMPL2
assignment while the obscure subset constitutes a blind test for which the answer was known but
not revealed at the time when the challenge was given. For the investigatory subset, the reference
data are either absent or evaluated only qualitatively, and the purpose of this exercise is to
predict them quantitatively using existing theoretical techniques. Figure 2 shows the molecular
structures of all compounds involved in Task 2.
FIGURE 2
TABLE 4
TABLE 5
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Table 4 compares the difference between the free energies of the two tautomers for each
compound in the obscure and explanatory subsets as calculated in the gas phase and in aqueous
solution using the SM8, SM8AD, and SMD continuum solvation models, to the corresponding
reference data in aqueous solution. The SM8AD model achieves the lowest mean unsigned errors
in all three cases of the obscure subset with respect to the corresponding experimental data
(Table 4). The SM8, SM8AD, and SMD models predict the dominant tautomer correctly for six
tautomeric pairs in the obscure subset but fail to predict the dominant tautomer qualitatively for
the tautomer pair 4A and 4B and for 6A and 6Z. Concerning the latter pair, the failure of our
models can be related to the zwitterionic nature of 6Z which cannot be described adequately by
the methods used in the present study. According to the SAMPL2 manual for Task 2
(Tautomeric Teasers), the corresponding equilibrium constant in the case of 5B and 5C is known
to be very sensitive to solvent variation. Indeed, all the models tested in this study confirm that
the difference in the free energies of 5B and 5C in aqueous solution can differ from that in the
gas phase by factors of 5 – 9 (Table 4). All of our models predict the reference data for case 4
(cis and trans-α-diketones) and case 6 (xanthine tautomerism) in the explanatory subset
quantitatively correctly (within the given uncertainties of the corresponding experimental
energies). To the contrary, the tested models fail to qualitatively reproduce the dominant
tautomer for five out of ten tautomeric pairs in case 5 (pyrazolones and isoxazolones). We
investigated the failure of our models in regard to case 5 as well as in regard to the tautomeric
pair 6A and 6Z in view of the possible error in the M06-2X/MG3S gas-phase free energies for
the corresponding molecules. Table 5 compares the free energy differences for the problematic
tautomeric pairs calculated using the M06-2X/MG3S//M06-2X/MG3S gas-phase free energies to
those calculated using the BMC-CCSD//M06-2X/MG3S gas-phase free energies. In general, the
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BMC-CCSD method does not improve the resulting free energy differences for the given
tautomeric pairs in solution, producing even larger errors as compared to M06-2X/MG3S. Thus
we conclude that the failure of our methods to correctly predict the reference data for the given
tautomeric pairs in aqueous solution can be attributed to the inaccuracy of our solvation models
for these particular cases. However, some of the reference data were evaluated using empirical
linear structure energy relationship techniques involving the use of empirical solvent parameters
to derive solute-specific equations for equilibrium constants. Therefore, one can speculate that
the uncertainty in the corresponding reference data can be larger than previously estimated (0.1 –
0.7 kcal/mol in Table 5). On the other hand, we notice very good agreement with the
experimental value for the tautomeric pair 16A and 16C (Table 4) obtained by direct UV
observation [39] which is the most accurate datum for case 5. It would also be interesting to
examine solvent clustering in these instances, but we did not undertake this task.
TABLE 6
Table 6 presents the free energy difference predicted for the corresponding tautomers in
the investigatory subset for which the experimental tautomeric ratios are known at least
qualitatively. Tetronic acids (20A/B.o) are believed to be enolized in solution, and this
assumption is confirmed by SM8 and SM8AD. The SMD model predicts that the diketone form
is slightly dominating. Substitution of oxygen by sulfur results in a stronger preference for the
enolized form, whereas the addition of an N-methyl or a CH2 group results in the contrary trend
with all of the tested models. Case 8 comprises cyclic lactams and similar compounds. All our
models correctly predict that the oxo-form should be dominant in aqueous solution. Case 9
comprises cyclic triketones for many of which our models predict that their tautomeric ratios in
aqueous solution are close to those in the gas phase in accord with a suggestion given in the
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SAMPL2 manual that the cyclic triketones can be highly polar and their polarity is likely to
remain the same between tautomers and, therefore, their tautomeric ratios may not be affected by
solvation. Case 10 involves the nitrogen-nitrogen tautomerism in compounds with bridgehead
nitrogen. Our results indicate that for the tautomeric pair 29A and 29B and for 31A and 31B the
solvation effects favor the enolized (B) form whereas for the tautomeric pair 28A and 28B and
30A and 30B the solvation effects only slightly influence the tautomeric ratio as well as for
diazepines (case 11). For five membered ring 2-oxoheterocycles involved in case 12, all three
models reasonably agree with one another and predict correctly (in accord with the SAMPL2
manual) that tautomer 35C is dominant, regardless of the substituent (z = N, O, or N-CH3). With
respect to the 35A.x_35B.x tautomerism, our results indicate that solvation is not the major
factor in the process, and the ketone form is predicted to be dominant in both the gas phase and
aqueous solution, regardless of the nature of the heteroatom z.
Conclusion
The quantum mechanical continuum solvent models SM8, SM8AD, and SMD predict
experimental aqueous free energies of solvation (vacuum-water transfer free energies) for 30 out
of 31 polyfunctional compounds involved in the SAMPL2 test set with mean unsigned errors of
1.4 (SM8), 2.0 (SM8AD), and 2.6 kcal/mol (SMD). Mean unsigned errors in the free energy
differences (tautomeric ratios) for 21 tautomeric pairs in aqueous solution tested in the present
study are 2.7 (SM8), 1.8 (SM8AD), and 2.4 kcal/mol (SMD). Given the complex character of the
compounds involved in the SAMPL2 challenge as well as in view of the possibility of larger than
reported uncertainties in several reference data (especially, for the tautomer ratios), all three
models tested in the present work perform well. Nevertheless, further improvement of these
19
models will merit consideration, especially with respect to improving the representation of
zwitterionic functionality in existing training sets.
Given our comparison of SM8, SM8AD, and SMD, it is natural to inquire as to whether
one is clearly to be preferred over the others. The significant variation in mean unsigned errors
over the molecular and tautomeric test sets noted above does not provide a single endorsement,
however—SM8 clearly outperforms SM8AD and SMD for the former set while SM8AD does
best for the latter. We have already noted that we consider uncertainty in the experimental data to
remain too high to consider the observed differences to be decisive. Moreover, the test sets
themselves are not especially diverse, so that model differences may be associated more with
individual functionalities (e.g., the better performance of SM8AD for oxidized sulfur
functionality, which derives from its training on a test set that had better representation of such
functional groups compared to SM8 and SMD). In addition, however, there may be other reasons
to choose one solvation model over another that are not readily tested by the SAMPL2 data. For
example, the SM8 and SM8AD models rely on underlying charge models that are used in the
computation of generalized Born electrostatic free energies of solvation, and such models have
been defined primarily for a set of balanced, medium-sized basis sets; by contrast, SMD does not
depend on a charge model, and thus it may be used with more extended basis sets or with basis
sets for which a charge model just does not happen be available. Similarly, by construction, we
expect SM8AD to be more accurate for large solutes with complex shapes having very
asymmetric charge distributions. And, of course, individual users may have empirically observed
one model to be more effective than another for certain classes of problems, or such observations
may have been made in the literature. Thus, rather than recommend a single model as the “best”
20
for all situations, we encourage users to consider all of the above factors when making a choice
of SMx model and proceed accordingly.
Acknowledgements. This work was supported by the Office of Naval Research under Grant
N 00014-05-01-0538, the Army Research Office under Grant US ARMY RES LAB/W911NF09-
1-0377, and the National Science Foundation (Grant CHE06-10183 and Grant CHE07-04974).
Computational resources were provided by Minnesota Supercomputing Institute.
References
1 Bamborough P, Cohen FE (1996) Modeling protein-ligand complexes. Curr Opin Struct Biol
6(2):236-241
2 Pei J, Wang Q, Zhou J, Lai, L (2004) Estimating protein-ligand binding free energy: Atomic
solvation parameters for partition coefficient and solvation free energy calculation. Proteins
54(4):651-664
3 Schiffer CA, Caldwell JW, Stroud RM, Kollman PA (1992) Inclusion of solvation free
energy with molecular mechanics: alanyl dipeptide as a test case. Protein Sci 1(3):396-400
4 Kollman P (1993) Free energy calculations: applications to chemical and biochemical
phenomena. Chem Rev 93(7):2395-2417
5 Rivail J-L, Rinaldi DL, Ruiz-Lopez MF The self-consistent reaction field model for
molecular computations in solution. In Formosinho SJ, Arnaut L, Csizmadia I (eds),
Theoretical and computational models for organic chemistry, Kluwer Academic Publishers,
1991, pp 79-92
21
6 Tomasi J, Persico M (1994) Molecular interactions in solution: an overview of methods
based on continuous distributions of the solvent. Chem Rev 94(7):2027-2094
7 Hawkins GD, Zhu T, Li J, Chambers CC, Giesen DJ, Liotard DA, Cramer CJ, Truhlar DG
Universal solvation models. In Gao J, Thompson MA (eds), Combined quantum mechanical
and molecular mechanical methods, American Chemical Society, Symposium Series,
Volume 712, Washington, DC, 1998, pp 201-219
8 Cramer CJ, Truhlar DG (1999) Implicit solvation models: equilibria, structure, spectra, and
dynamics. Chem Rev 99(8):2161-2200
9 Tomasi J, Mennucci B, Cammi R (2005) Quantum mechanical continuum solvation models.
Chem Rev 105(8):2999-3094
10 Mennucci B, Cammi R (eds) Continuum solvation models in chemical physics: from theory
to applications, Wiley, New York, 2008
11 Hoijtink GJ, de Boer E, van der Meij PH, Weijland WP (1956) Reduction potentials of
various aromatic hydrocarbons and their univalent anions. Recueil des Travaux Chimiques
des Pays-Bas et de la Belgique 75: 487-503
12 Tucker SC, Truhlar DG (1989) Generalized born fragment charge model for solvation effects
as a function of reaction coordinate. Chem Phys Lett 157(1-2): 164-170
13 Still WC, Tempczyk A, Hawley RC, Hendrickson T (1990) Semianalytical treatment of
solvation for molecular mechanics and dynamics. J Am Chem Soc 112(16):6127-6129
14 Marenich AV, Olson RM, Kelly CP, Cramer CJ, Truhlar DG (2007) Self-consistent reaction
field model for aqueous and nonaqueous solutions based on accurate polarized partial
charges. J Chem Theory Comput 3(6):2011-2033
22
15 Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on the
generalized Born approximation with asymmetric descreening. J Chem Theory Comput
5(9):2447-2464
16 Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on solute
electron density and a continuum model of the solvent defined by the bulk dielectric constant
and atomic surface tensions. J Phys Chem B 113(18):6378-6396
17 Tomasi J, Mennucci B, Cancès E (1999) The IEF version of the PCM solvation method: an
overview of a new method addressed to study molecular solutes at the QM ab initio level. J
Mol Struct (Theochem) 464(1):211-226
18 Grycuk T (2003) Deficiency of the coulomb-field approximation in the generalized Born
model: an improved formula for Born radii evaluation. J Chem Phys 119(9):4817-4826
19 Storer JW, Giesen DJ, Cramer CJ, Truhlar DG (1995) Class IV charge models: a new
semiempirical approach in quantum chemistry. J Comp-Aided Mol Des 9:87-110
20 Kelly CP, Cramer CJ, Truhlar DG (2005) SM6: A density functional theory continuum
solvation model for calculating aqueous solvation free energies of neutrals, ions, and solute-
water clusters. J Chem Theory Comput 1(6):1133-1152
21 Olson RM, Marenich AV, Cramer CJ, Truhlar DG (2007) Charge Model 4 and
intramolecular charge polarization. J Chem Theory Comput 3(6):2046-2054
22 Baldridge K, Klamt A (1997) First principles implementation of solvent effects without
outlying charge error. J Chem Phys 106:6622-6633
23 Marenich AV, Cramer CJ, Truhlar DG (2009) Performance of SM6, SM8, and SMD on the
SAMPL1 test set for the prediction of small-molecule solvation free energies. J Phys Chem B
113(14):4538-4543
23
24 Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main
group thermochemistry, kinetics, noncovalent interactions, excited states, and transition
elements: two new functionals and systematic testing of four M06 functionals and twelve
other functionals. Theor Chem Acc 120:215-241
25 Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, DeFrees DJ, Pople JA (1982)
Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-
row elements. J Chem Phys 77:3654-3666
26 Hariharan PC, Pople JA (1973) The influence of polarization functions on molecular orbital
hydrogenation energies. Theoret Chimica Acta 28(3):213-222
27 Lynch BJ, Zhao Y, Truhlar DG (2003) Effectiveness of diffuse basis functions for
calculating relative energies by density functional theory. J Phys Chem A 107(9):1384-1388
28 Bryantsev VS, Diallo MS, Goddard WA (2008) Calculation of solvation free energies of
charged solutes using mixed cluster/continuum models. J Phys Chem B 112:9709-9719
29 Lynch BJ, Zhao Y, Truhlar DG (2005) The 6-31B(d) basis set and the BMC-QCISD and
BMC-CCSD multicoefficient correlation methods. J Phys Chem A 109(8):1643-1649
30 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery
Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V,
Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M,
Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene
M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R,
Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY,
Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels
AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV,
24
Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P,
Komaromi I. Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A,
Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA,
Gaussian03, revision E.01, Gaussian, Inc., Pittsburgh, PA, 2003.
31 MN-GFM: Minnesota Gaussian Functional Module, version 4.1; University of Minnesota:
Minneapolis, MN, 2008
32 MN-GSM: Minnesota Gaussian Solvation Module, version 2009; University of Minnesota:
Minneapolis, MN, 2009
33 Halgren TA (1996) Merck molecular force field. I. Basis, form, scope, parameterization, and
performance of MMFF94. J Comp Chem 17(5):490-519
34 PCModel, version 9.1 for Windows, 2006, Serena Software, Bloomington, IN 47402
35 Adamo C, Barone V (1998) Exchange functionals with improved long-range behavior and
adiabatic connection methods without adjustable parameters: The mPW and mPW1PW
models. J Chem Phys 108(2):664-676
36 Easton RE, Giesen DJ, Welch A, Cramer CJ, Truhlar DG (1996) The MIDI! basis set for
quantum mechanical calculations of molecular geometries and partial charges. Theor Chim
Acta 93(5):281-301
37 Kelly CP, Cramer CJ, Truhlar DG (2006) Adding explicit solvent molecules to continuum
solvent calculations for the calculation of aqueous acid dissociation constants. J Phys Chem
A 110(7):2493-2499
38 Ribeiro RF, Marenich AV, Cramer CJ, Truhlar DG (2009) Solvent dependence of 14N
nuclear magnetic resonance chemical shielding constants as a test of the accuracy of the
25
computed polarization of solute electronic densities by the solvent. J Chem Theory Comput
5(9):2284-2300
39 Katritzky AR, Øksne S, Boulton AJ (1962) The tautomerism of heteroaromatic compounds
with five-membered rings – III: Further isoxazol-5-ones. Tetrahedron 18(6):777-790
26
TABLE 1: Aqueous free energies of solvation (kcal/mol) for the obscure and explanatory
SAMPL-09 sets a
compound SM8 SM8AD SMD expobscure subset
uracil –16.76 –16.56 –14.15 –16.59 ± 0.285-bromouracil –16.39 –16.74 –14.09 –18.17 ± 0.555-chlorouracil –16.59 –14.09 –14.34 –17.74 ± 0.785-fluorouracil –17.38 –16.69 –13.88 –16.92 ± 0.885-trifluoromethyluracil –16.52 –16.30 –13.46 –15.46 ± 0.166-chlorouracil –14.24 –14.09 –11.32 –15.83 ± 1.22cyanuric acid –20.32 –17.90 –14.77 –18.26 ± 0.27caffeine –11.90 –12.36 –10.34 –12.64 ± 0.74methyl paraben –9.85 –11.38 –9.09 –9.51 ± 0.26ethyl paraben –9.50 –10.92 –9.17 –9.20 ± 0.30propyl paraben –9.24 –10.60 –9.01 –9.37 ± 0.22butyl paraben –8.42 –9.54 –8.36 –8.72 ± 0.27acetylsalicylic acid –11.93 –13.98 –11.12 –9.94 ± 0.18diflunisal –13.96 –16.41 –14.38 –9.40 ± 0.20flurbirprofen –9.03 –10.46 –9.26 –8.42 ± 0.16ibuprofen –6.88 –7.54 –7.42 –7.00 ± 0.64ketoprofen –12.56 –16.42 –12.91 –10.78 ± 0.18naproxen –10.90 –12.61 –11.29 –10.21 ± 0.18phthalimide –11.99 –11.75 –8.61 –9.61 ± 0.50sulfolane –13.26 –7.10 –12.29 –8.61 ± 0.31D-glucose –25.29 –29.27 –36.00 –25.47 ± 0.22D-xylose –21.71 –24.98 –28.31 –20.52 ± 0.27MUE 1.28 2.17 2.73
explanatory subset hexachlorobenzene –0.23 –1.01 1.39 –2.30 ± 1.16hexachloroethane –0.04 –0.70 1.24 –1.41 ± 0.10octafluorocyclobutane 3.60 3.82 4.42 3.01 ± 0.03trimethyl o-trifluoroacetate –1.67 –3.61 –0.67 –0.80 ± 0.20trimethyl phosphate –7.46 –10.18 –7.45 –8.70 ± 0.104-nitroaniline –10.48 –12.00 –9.30 –10.01 ± 0.11glycerol b –11.71 –12.20 –11.65 –13.40 ± 1.00pentachloronitrobenzene –1.73 –2.08 1.41 –5.22 ± 0.25MUE 1.47 1.68 2.28 RMSE c 1.78 2.61 3.54 MUE c 1.33 2.04 2.61 MSE c –0.24 –0.95 0.43
27
a Experimental aqueous free energies of solvation (or vacuum-water free energies of transfer)
were provided by OpenEye Scientific Software. Theoretical (SM8, SM8AD, and SMD) aqueous
free energies were calculated using the Cartesian geometries provided by OpenEye Scientific
Software unless noted otherwise. RMSE, MUE, and MSE refer to root mean squared error, mean
unsigned error, and mean signed error, respectively. Note that we excluded 1-iodouracil
originally present in the obscure subset from consideration here because the tested solvation
models were not parameterized for iodine-containing compounds.
b Calculated using a re-optimized geometry as discussed in the text; the aqueous free energies of
solvation calculated using OpenEye’s Cartesian geometries are –17.0 (SM8), –18.8 (SM8AD),
and –21.0 (SMD) kcal/mol.
c Calculated by summation over the 30 compounds of the obscure and explanatory subsets (see
also a comment on 1-iodouracil in footnote a)
28
TABLE 2: Aqueous free energies of solvation (kcal/mol) for the investigatory SAMPL2 set a
compound SM8 SM8AD SMDhexamethylphosphoramide –7.47 –9.91 –10.19dimethyl methylphosphonate –9.53 –11.22 –10.09methyl dimethylphosphinate –9.79 –12.34 –12.81methyl phenyl sulfoxide –11.53 –10.24 –9.21trifluoromethyl phenyl sulfoxide –7.63 –5.52 –4.76methyl phenyl sulfone –13.55 –8.54 –11.79trifluoromethyl phenyl sulfone –8.32 –2.11 –5.20oxazole –5.94 –4.58 –3.88thiazole –4.86 –4.84 –4.15isothiazole –6.22 –5.92 –3.98
a SM8, SM8AD, and SMD aqueous free energies of solvation (or vacuum-water free energies of
transfer) were calculated using the Cartesian geometries provided by OpenEye Scientific
Software.
29
TABLE 3: Aqueous free energies of solvation (kcal/mol) for selected compounds calculated with
and without adding explicit water molecules a
compound SM8 SM8/C SM8AD SM8AD/C SMD SMD/C exphexachlorobenzene –0.23 –0.78 –1.01 –1.29 1.39 0.81 –2.30hexachloroethane -0.04 –1.65 –0.70 –2.03 1.24 –0.64 –1.41octafluorocyclobutane 3.60 4.55 3.82 4.52 4.42 4.05 3.01trimethyl o-trifluoroacetate –1.67 –1.50 –3.61 –3.23 –0.67 –1.34 –0.80trimethyl phosphate –7.46 –7.15 –10.18 –11.17 –7.45 –8.66 –8.704-nitroaniline –10.48 –12.81 –12.00 –14.77 –9.30 –10.62 –10.01pentachloronitrobenzene –1.73 –0.70 –2.08 –0.86 1.41 1.90 –5.22MUE 1.47 1.61 1.68 2.45 2.28 1.65
a Experimental aqueous free energies (exp) of solvation (or vacuum-water free energies of
transfer) were provided by OpenEye Scientific Software. The SM8, SM8AD, and SMD aqueous
free energies of solvation for unclustered solutes were calculated without adding explicit water
molecules. The SM8/C, SM8AD/C, and SMD/C aqueous free energies of solvation for
unclustered solutes were calculated by Eq. 2 using the calculated free energies of solvation of the
corresponding water-solute clusters. MUE refers to mean unsigned error.
30
TABLE 4: Free energy difference (kcal/mol) for tested tautomeric pairs in the obscure and
explanatory subsets a
tautomeric pair gas SM8 SM8AD SMD exp b obscure subset
case 1 1A_1B –3.5 –1.7 –3.0 –1.9 –4.8 ± 0.32A_2B –8.3 –5.1 –6.1 –5.7 –6.1 ± 0.33A_3B –4.4 –5.7 –6.7 –6.6 –7.2 ± 0.34A_4B 3.2 2.3 0.8 2.3 –2.3 ± 0.4MUE 2.6 1.3 2.1
case 2 5A_5B –4.7 –3.4 –4.4 –2.8 –4.8 ± 0.55B_5C 8.7 1.0 1.5 1.9 0.5 ± 0.2MUE 0.9 0.7 1.7
case 3 6A_6Z 10.7 2.0 0.8 2.0 –2.4 ± 0.36A_6B –10.7 –8.4 –9.7 –9.5 –9.2 ± 0.4MUE 2.6 1.9 2.3
explanatory subset case 4
7A_7B 9.3 7.1 6.5 6.8 7.0 ± 1.58A_8B –4.2 –2.9 –2.9 –2.9 –3.0 ± 3.0MUE 0.1 0.3 0.1
case 5 10B_10C 2.5 1.1 0.0 0.9 –2.9 ± 0.410D_10C 3.1 4.5 2.6 4.1 –1.2 ± 0.211D_11C 4.9 5.8 4.0 4.5 –0.5 ± 0.212D_12C 6.9 5.3 3.1 3.7 –1.8 ± 0.713D_13C 3.2 4.8 3.3 3.5 0.1 ± 0.114D_14C 3.1 2.0 0.8 2.1 0.3 ± 0.315A_15B 4.4 3.1 3.6 3.0 0.9 ± 0.315A_15C 5.3 2.9 2.3 2.0 –1.2 ± 0.315B_15C 0.9 –0.2 –1.2 –1.0 –2.2 ± 0.316A_16C 3.1 0.4 0.4 1.8 0.5 ± 0.1MUE 3.8 2.7 3.3
case 6 17F_17B 8.1 4.3 3.6 2.3 3.4 RMSE c 3.4 2.4 3.0
MUE c 2.7 1.8 2.4
MSE c 2.7 1.7 2.3
31
Footnote to TABLE 4
a Notations used in the table for tautomeric pairs refer to the notations given in the SAMPL2
manual. For example, the notation M1_M2 refers to the free energy of the M1 → M2 reaction
defined as the difference between the free energy of tautomer M2 and the free energy of
tautomer M1. The SM8, SM8AD, and SMD free energy differences between two tautomeric
forms in aqueous solution were calculated using the SM8, SM8AD, and SMD continuum
solvation models, respectively. The free energy difference between two tautomeric forms in the
gas phase was calculated as well (“gas”). MUE refers to mean unsigned error.
b SAMPL2 reference data evaluated from the corresponding experimental tautomeric ratios in
aqueous solution and provided by OpenEye Scientific Software.
c RMSE, MUE, and MSE refer to root mean squared error, mean unsigned error, and mean
signed error, respectively, calculated over all 21 data.
32
TABLE 5: Comparison of the free energy difference (kcal/mol) for selected tautomeric pairs
calculated using the M06-2X/MG3S and BMC-CCSD//M06-2X/MG3S methods a
tautomeric pair M06-2X/MG3S BMC-CCSD//M06-2X/MG3S exp b gas SM8 SM8AD SMD gas SM8 SM8AD SMD
case 3 6A_6Z 10.7 2.0 0.8 2.0 13.5 4.7 3.6 4.7 –2.4 ± 0.36A_6B –10.7 –8.4 –9.7 –9.5 –15.9 –13.5 –14.8 –14.6 –9.2 ± 0.4MUE 2.6 1.9 2.3 5.8 5.7 6.3
case 5 10B_10C 2.5 1.1 0.0 0.9 2.4 1.0 –0.1 0.8 –2.9 ± 0.410D_10C 3.1 4.5 2.6 4.1 3.3 4.6 2.8 4.3 –1.2 ± 0.211D_11C 4.9 5.8 4.0 4.5 5.0 5.9 4.2 4.6 –0.5 ± 0.212D_12C 6.9 5.3 3.1 3.7 6.8 5.2 3.1 3.6 –1.8 ± 0.713D_13C 3.2 4.8 3.3 3.5 3.4 5.0 3.5 3.7 0.1 ± 0.114D_14C 3.1 2.0 0.8 2.1 3.8 2.7 1.5 2.8 0.3 ± 0.315A_15B 4.4 3.1 3.6 3.0 5.2 3.9 4.4 3.8 0.9 ± 0.315A_15C 5.3 2.9 2.3 2.0 6.2 3.8 3.3 3.0 –1.2 ± 0.315B_15C 0.9 –0.2 –1.2 –1.0 1.0 0.0 –1.1 –0.9 –2.2 ± 0.316A_16C 3.1 0.4 0.4 1.8 4.5 1.8 1.8 3.3 0.5 ± 0.1MUE 3.8 2.7 3.3 4.2 3.1 3.7
a See footnote a to Table 4 and the main text for more detail
b See footnote b to Table 4
33
TABLE 6: Free energy difference (kcal/mol) for tested tautomeric pairs in the investigatory
subset a
tautomeric pair gas SM8 SM8AD SMDcase 7
19A.h_19B.h 1.5 0.5 0.4 0.120A.ch2_20B.ch2 4.9 1.2 0.7 0.220A.o_20B.o 2.8 –0.2 –0.7 0.220A.s_20B.s 2.3 –1.8 –2.4 –1.820A.nch3_20B.nch3 4.7 1.8 1.5 2.921A_21B 13.9 13.0 12.7 12.7
case 8 22A_22B –10.1 –10.0 –11.5 –11.323A_23B –11.7 –10.9 –12.5 –11.824A_24B –21.8 –12.8 –14.1 –13.525A_25B –25.5 –15.1 –16.7 –14.226A_26B –19.8 –15.6 –17.1 –16.2
case 9 27A.o_27B.o –0.9 –1.0 –0.1 –0.227A.o_27C.o 0.4 –1.0 –0.3 –0.227A.o_27D.o 13.4 7.1 7.8 7.227A.s_27B.s 0.2 0.3 0.2 2.127A.s_27C.s 14.1 6.4 4.8 6.527A.s_27D.s 16.5 10.9 9.4 11.327A.nh_27B.nh –0.8 –0.4 –0.2 –0.427A.nh_27C.nh 1.5 0.6 1.0 0.627A.nh_27D.nh 1.8 1.5 1.5 0.5
case 10 28A_28B 0.1 0.4 0.6 0.529A_29B 3.7 –0.8 –0.1 0.130A_30B –4.0 –4.0 –3.0 –3.531A_31B –2.3 –6.9 –5.8 –5.9
case 11 32A_32B –9.3 –9.6 –8.9 –8.633A_33B 11.2 10.0 10.5 10.634A_34B 5.1 4.5 5.0 4.7
34
TABLE 6: Continued a
tautomeric pair gas SM8 SM8AD SMDcase 12
35C.nch3_35A.nch3 –0.3 2.4 2.8 1.535A.nch3_35B.nch3 6.4 5.9 6.4 5.435C.o_35A.o 1.8 4.8 5.0 4.235A.o_35B.o 9.0 8.9 8.8 8.135C.s_35A.s 2.8 4.7 4.9 4.435A.s_35B.s 3.2 2.6 2.3 1.8
a See footnote a to Table 4 and the main text for more detail
35
hexachlorobenzene hexachloroethane
octafluorocyclobutane trimethyl o-trifluoroacetate
trimethyl phosphate 4-nitroaniline
pentachloronitrobenzene
Figure1: Water-solute clusters for selected solutes involved in Task 1.
43
33B 34A 34B
case 12
35A-NCH3 35A-O 35A-S
35B-NCH3 35B-O 35B-S
35C-NCH3 35C-O 35C-S Figure 2: Molecular structures for solutes involved in Task 2.
1
Electronic supplementary information (ESI)
For
Reactivity of Copper(II)-Alkylperoxo Complexes
Tetsuro Tano,a Mehmed Z. Ertem,b Satoru Yamaguchi,c Atsushi Kunishita,a Hideki Sugimoto,a
Nobutaka Fujieda,a Takashi Ogura,*c Christopher J. Cramer*b and Shinobu Itoh*a
aDepartment of Material and Life Science, Division of Advanced Science and Biotechnology,
Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
E-mail: shinobu@mls.eng.osaka-u.ac.jp bDepartment of Chemistry and Research Computing Center, University of Minnesota, 207 Pleasant
St. SE, Minneapolis, MN 55455, USA. E-mail: cramer@umn.edu cResearch Institute of Picobiology, Graduate School of Life Science, University of Hyogo, 3-2-1
Kouto, Kamigori-cho, Ako-gun, Hyogo 678-1297, Japan. E-mail: ogura@sci.u-hyogo.ac.jp
2
Fig. S1
2.0
1.5
01
[CmOOH] / mM
Abs
388
0 2
0.5
1.0
3
(a)
4
8
6
2
00 2 4 6 10
104{[CmOOH]0–[Cu]0(A–A0)/(A∞–A0)} / M
(A–A
0)/(A
∞–A
)
4
(b)
8
Fig. S1. (a) Spectrophotometric titration for the formation of cumylperoxo copper(II) complex from the reaction of 1aH (1.0 mM) and CmOOH in the presence of Et3N (10 mM) in CH3CN at –40ºC. (b) Plot of (A – A0)/(A∞ – A) against [[CmOOH]0–[Cu]0(A – A0) /(A∞ – A0)].
3
Fig. S2 and S3
1.0
0.8
0.6
0300 500 800 1000
430
Wavelength / nm
Ab
so
rban
ce
400 600 700 900
0.2
0.4
Fig. S2 Spectral change for the reaction of 1b (1.0 mM) with CmOOH (2.5 mM) in the presence of Et3N (10 mM) in CH3CN at –40ºC.
0.8
0.6
01
[CmOOH] / mM
Abs
43
0
0 2
0.2
0.4
(a)
60
40
20
00 4 6 8
104{[CmOOH]0–[Cu]0(A–A!)/(A!–A0)} / M
(A–A
0)/
(A!–A
)
(b)
2
Fig. S3 (a) Spectrophotometric titration for the formation of cumylperoxo copper(II) complex from the reaction of 1b (1.0 mM) and CmOOH in the presence of Et3N (10 mM) in CH3CN at –40ºC. (b) (A – A0)/(A∞ – A) against {[CmOOH]0–[Cu]0(A – A0) /(A∞ – A0)}.
4
Fig. S4
500 505 510 515
m /z
504.2
EXP.
500 505 510 515
SIM.
500 505 510 515
m /z
508.2
EXP.
500 505 510 515
SIM.
506.2
510.2
m /z m /z
(a) (b)
Fig. S4 Experimental (bottom) and simulated (top) peak envelopes in the positive-ion ESI-MS spectra of the product derived from the reaction of 1b (1.0 mM) with CmOOH (1.0 mM) in the presence of Et3N (1.0 mM) in CH3CN at –40ºC; (a) with Cm16O2H and (b) with Cm18O2H.
5
Fig. S5
858
589
600 900
528
Wavenumber / cm–1
500 700 800
797
S
879
607535
832
S
400
Fig. S5 Resonance Raman spectra of the product derived from the reaction of 1b (4.0 mM) with CmOOH (12 mM) in the presence of Et3N (40 mM) generated by using Cm16O2H (solid line, below) and Cm18O2H (doted line, above) obtained with λex = 441.6 nm in CH3CN –40℃; s denotes the solvent band.
6
Fig. S6
Fig. S6 (a) ESR spectrum of 1b (starting material) (2.0 x 10–3 M) in CH3CN at –196℃. ESR parameter g⊥ = 2.112. (b) ESR spectrum of the 2b generated in the reaction of 1b (2.0 x 10–3 M) and CmOOH (1.0 x 10–2 M) in the presence of Et3N (2.0 x 10–3 M) in CH3CN at –196℃. ESR parameters g⊥ = 2.118. Low resolution of the spectrum prohibits precise assignment of the g// value.
7
Fig. S7
350 360 370 380
m / z
352.2
354.2
369.2
378.2
371.2
(a)
(b)
(c)
380.2
Figure S7. ESI-MS (pos.) spectrum after the self-decomposition of 2aH in CH3CN. (a) m/z =
352.2 ([CuI(bpaH)]+), (b) m/z = 369.2 ([CuII(bpaH)(OH)]+), (c) m/z = 378.2 ([CuII(bpaH)(CN)]+).
8
Fig. S8
Fig. S8 HPLC diagram of the self-decomposition products of 2a. Peak 1: cumyl alcohol (CmOH); peak 2: acetophenone (PhCOMe); peak 3: anisole (internal standard material).
9
Fig. S9
Fig. S9 HPLC diagram of the self-decomposition products of 2b. Peak 1: cumyl alcohol (CmOH); peak 2: acetophenone (PhCOME); peak 3: anisole (internal standard material).
10
Fig. S10
350 360 370 380
m / z
351.8
353.8
368.8
377.8
(a)
(b)
(c)
Fig. S10 ESI-MS (pos.) spectrum of the final reaction mixture of 2a and CHD. (a) m/z = 351.8 ([CuI(bpa)]+), (b) m/z = 368.8 ([CuII(bpa)(OH)]+), (c) m/z = 377.8 ([CuII(bpa)(CN)]+).
11
Fig. 11
Fig. S11 HPLC diagram of the products derived from the reaction of 2a and CHD. Peak 1: cumyl alcohol (CmOH); peak 2: acetophenone (PhCOMe) ; peak 3: anisole (internal standard material); peak 4: benzene.
12
Fig. S12
Fig. S12 HPLC diagram of the products of derived from the reaction of 2b and CHD. Peak 1: cumyl alcohol (CmOH); peak 2: acetophenone (PhCOMe); peak 3: anisole (internal standard material); peak 4: benzene.
13
Fig. S13
0.5
0.3
0300 500 800
430
Wavelength / nm
Ab
so
rban
ce
400 600 700
0.1
900 1000
0.4
0.2
0.6
–2.5
4000Time / s
ln(A
-A!)
0
–2
2000 30001000
(a)
1.5
0.5
00 0.10
[CHD] / M
10
3k
ob
s /
s–1
0.05 0.15
1.0
(b)
Fig. S13 (a) Spectral change for the reaction of 2b (1.0 mM) and CHD (30 mM) in CH3CN at 30 °C under anaerobic conditions; Inset: the pseudo-first-order plot based on the absorption change at 430 nm. (b) Plots of kobs vs substrate concentration for the reaction of 2b with CHD.
14
DFT calculation results
I – Cartesian Coordinates (ang) and Energies (Eh, doublet electronic states)
1) – [CuII(bpa)(CH3CN)]2+
Energy: -1229.29162036 a.u.
C -1.90034300 -2.91672300 -0.40538600 C -1.59170000 -4.26747700 -0.36107500 C -0.40265500 -4.66204100 0.24649700 C 0.43989600 -3.69295600 0.78585100 C 0.06858400 -2.35762000 0.71358200 N -1.09166900 -1.98149700 0.12370600 H -0.12953700 -5.71357900 0.29426500 H -2.81073400 -2.55225200 -0.87499000 H -2.27131500 -4.99213000 -0.80015800 H 1.37853200 -3.96789800 1.26247100 C 0.87213900 -1.23935700 1.30959800 H 0.54770700 -1.06208700 2.34422700 H 1.94450600 -1.47578500 1.34735200 N 0.63393900 -0.00040100 0.53733000 C 0.87280900 1.23811200 1.31010500 H 1.94531500 1.47388400 1.34805200 H 0.54817300 1.06063000 2.34463500 C 0.06999200 2.35709000 0.71443600 C 0.44209100 3.69217800 0.78726000 N -1.09039500 1.98187900 0.12424800 C -0.39978800 4.66196100 0.24811400 H 1.38081200 3.96638300 1.26413500 C -1.89840300 2.91777600 -0.40466900 C -1.58895200 4.26832800 -0.35983200 H -0.12605100 5.71331900 0.29631300 H -2.80889200 2.55398500 -0.87462300 H -2.26802500 4.99355100 -0.79881100 C 1.36894100 -0.00033000 -0.79820300 H 1.00873500 0.88597000 -1.33590000 H 1.00851100 -0.88640500 -1.33612000 C 2.85992800 -0.00051800 -0.67821900 C 3.56836700 -1.20840500 -0.62993200 C 3.56862400 1.20720300 -0.62956500 C 4.95494000 -1.20899200 -0.52056300 H 3.03064500 -2.15485400 -0.71707800 C 4.95519500 1.20746700 -0.52019500 H 3.03110000 2.15379200 -0.71642200 C 5.64781700 -0.00084500 -0.45865300 H 5.49832700 -2.15071100 -0.50057500 H 5.49878100 2.14906400 -0.49992000 H 6.73242500 -0.00097200 -0.37991100 Cu -1.35882000 0.00029300 0.06167500 C -4.47374600 0.00129900 -0.47138200 N -3.31836200 0.00092300 -0.34882800 C -5.90467000 0.00155800 -0.62851100 H -6.34141000 -0.86207000 -0.11530300 H -6.33216900 0.91470300 -0.20031500
15
H -6.16863700 -0.04761200 -1.69063000
2) – [CuII(bpa)(CH3CN)2]2+
Energy: -1362.07096036 a.u.
C -1.52792500 -2.94647400 -0.90498000 C -1.18817200 -4.29052200 -0.85294900 C -0.06691300 -4.66756600 -0.11959300 C 0.67576800 -3.68832400 0.53477400 C 0.27366900 -2.36197800 0.44662200 N -0.81735900 -2.00231200 -0.26853200 H 0.23157600 -5.71177200 -0.06376000 H -2.38917600 -2.59655700 -1.46923200 H -1.78991300 -5.02237600 -1.38419700 H 1.56218700 -3.94695500 1.11049900 C 0.97261400 -1.23575100 1.15019600 H 0.49927300 -1.06452000 2.12687700 H 2.03318700 -1.45904600 1.33316500 N 0.81515300 0.00004100 0.35866700 C 0.97284900 1.23580200 1.15021100 H 2.03346400 1.45891400 1.33315000 H 0.49949500 1.06467400 2.12690200 C 0.27407000 2.36214600 0.44666700 C 0.67652000 3.68840000 0.53465600 N -0.81720600 2.00271500 -0.26823600 C -0.06606800 4.66778600 -0.11960100 H 1.56312300 3.94684000 1.11017900 C -1.52773100 2.94702300 -0.90453200 C -1.18761900 4.29098900 -0.85263700 H 0.23270800 5.71192000 -0.06391500 H -2.38924800 2.59733400 -1.46850700 H -1.78933800 5.02296300 -1.38375000 C 1.67537000 -0.00003300 -0.89088100 H 1.37109300 0.88472100 -1.46376300 H 1.37086600 -0.88466200 -1.46383000 C 3.14915600 -0.00022000 -0.62538300 C 3.84942700 -1.20695300 -0.50456200 C 3.84970200 1.20634400 -0.50448400 C 5.21800900 -1.20800200 -0.25440400 H 3.32188600 -2.15305900 -0.64315900 C 5.21828400 1.20706800 -0.25432900 H 3.32237900 2.15257900 -0.64302300 C 5.90153200 -0.00054900 -0.12319700 H 5.75596800 -2.15006800 -0.17792900 H 5.75645900 2.14900600 -0.17779500 H 6.97269300 -0.00067700 0.06474300 Cu -1.15835700 0.00023600 -0.23095700 C -3.90340500 0.00012300 -1.83264800 N -2.90084000 0.00034100 -1.24662100 C -2.61457200 -0.00033600 2.87691700 N -1.99571200 -0.00036500 1.89108200 C -3.37866100 -0.00012000 4.10199700 H -4.11557000 -0.80988100 4.09071600 H -2.71848700 -0.14289600 4.96384300 H -3.90609900 0.95193800 4.22141500 C -5.14643600 -0.00006300 -2.56204200 H -5.70610100 -0.91911100 -2.35782900
16
H -5.76148600 0.85574900 -2.26394400 H -4.95363800 0.06242500 -3.63850700
3) – [CuII(bpa)(CH3CN)(O2Cm)]+
3a (structure i in Figure 8)
Energy: -1729.49998905 a.u.
C -1.01104800 3.28802300 -1.24670200 C -1.90923300 4.30272900 -1.55229900 C -3.21226600 4.20607300 -1.07295100 C -3.57473500 3.10311300 -0.30447300 C -2.61912500 2.13216800 -0.02698700 N -1.36138000 2.23429400 -0.49830700 H -3.94414900 4.97745700 -1.30288000 H 0.02121300 3.27866100 -1.59603100 H -1.59249600 5.14376800 -2.16296900 H -4.58783800 2.99173500 0.07836700 C -2.88753800 0.92675000 0.83412000 H -2.59616300 1.15783100 1.86760400 H -3.95880000 0.67232600 0.84318200 N -2.05228500 -0.19582000 0.38968600 C -1.79495800 -1.19727300 1.42823200 H -2.64644900 -1.88073900 1.57260900 H -1.64612900 -0.65526000 2.37162100 C -0.54062700 -1.96115500 1.09955400 C -0.35450900 -3.28322600 1.48707500 N 0.41279200 -1.28028800 0.42525400 C 0.84694900 -3.91920600 1.18742800 H -1.14919000 -3.80332200 2.01939700 C 1.56217900 -1.90292300 0.11946600 C 1.82239200 -3.21611700 0.48961900 H 1.01089600 -4.95266200 1.48556300 H 2.27869800 -1.30733500 -0.44294400 H 2.77382900 -3.66730400 0.21937300 C -2.54163800 -0.80338500 -0.89077400 H -1.76961400 -1.51743200 -1.20596900 H -2.54947400 0.00760500 -1.63099700 C -3.88525500 -1.46690900 -0.80671300 C -5.05563800 -0.74267500 -1.06079200 C -3.99311200 -2.81913400 -0.46247000 C -6.30393400 -1.34943600 -0.95735400 H -4.98198500 0.30276900 -1.36751700 C -5.23976500 -3.42890100 -0.35735000 H -3.08538700 -3.40415700 -0.30041200 C -6.39715100 -2.69257600 -0.60005400 H -7.20520100 -0.77720200 -1.16781300 H -5.30841300 -4.48352300 -0.09839300 H -7.37199000 -3.16976500 -0.52515800 Cu -0.13110700 0.65587200 -0.03812600 C 0.58630500 1.88013500 3.11528300 N -0.10665300 1.32530900 2.36004200 C 1.45433200 2.56683100 4.04575500 H 1.78696100 3.51998100 3.62155200 H 0.93039400 2.76698400 4.98593700 H 2.33731400 1.95554300 4.26011100
17
O 1.34149800 1.60085400 -0.74757800 O 2.41217100 0.73060300 -1.07971100 C 3.62805300 1.07842900 -0.32958300 C 3.30777700 1.21161100 1.14876700 H 2.84857300 0.29780300 1.54975500 H 4.21589000 1.42850200 1.72302600 H 2.60491300 2.03834300 1.28239200 C 4.16427500 2.39457400 -0.87786200 H 5.08690400 2.68461000 -0.36198700 H 4.38319700 2.31534800 -1.94742100 H 3.41844200 3.18464700 -0.73490900 C 4.53321600 -0.09410000 -0.66424600 C 5.14473600 -0.87922400 0.31737700 C 4.72836800 -0.43414200 -2.00972500 C 5.93886100 -1.96912800 -0.03505600 H 5.01018100 -0.64232100 1.37139700 C 5.50957700 -1.52904500 -2.36209700 H 4.24478600 0.15891700 -2.78422900 C 6.12042400 -2.29988400 -1.37461500 H 6.41849600 -2.55992000 0.74359300 H 5.64616900 -1.77919200 -3.41253400 H 6.74037800 -3.15108600 -1.64952800
3b
Energy: -1729.50013576 a.u.
C 0.94054800 3.53998900 0.14988500 C 1.81482300 4.61441500 0.25425200 C 3.13504400 4.44185400 -0.15017300 C 3.53807200 3.20618500 -0.65048600 C 2.60527100 2.18030000 -0.73884600 N 1.33095500 2.35641200 -0.33991700 H 3.84805100 5.25967400 -0.07189200 H -0.10549400 3.58800700 0.45114300 H 1.46537100 5.56310700 0.65211800 H 4.56372500 3.03641400 -0.97339500 C 2.90520200 0.82712200 -1.32450000 H 2.60032000 0.82508800 -2.38071600 H 3.98400400 0.60977700 -1.30650400 N 2.11784800 -0.20501900 -0.63317700 C 1.84557100 -1.38793800 -1.46011600 H 2.70706100 -2.07177000 -1.51143500 H 1.65603000 -1.03826900 -2.48519400 C 0.61993000 -2.09471900 -0.94981000 C 0.47892100 -3.47693600 -0.98767100 N -0.35948700 -1.29494800 -0.47714700 C -0.70678800 -4.05133500 -0.53811400 H 1.29248000 -4.09078600 -1.37017900 C -1.49277100 -1.85199100 -0.02456600 C -1.71111400 -3.22353300 -0.04845500 H -0.83874600 -5.13088100 -0.56370000 H -2.24019000 -1.15141300 0.34680000 H -2.65445000 -3.62238600 0.31568800 C 2.69254100 -0.55952100 0.70798600 H 1.95820100 -1.21691400 1.18913100 H 2.69691700 0.36989800 1.29089400 C 4.05298600 -1.19038700 0.66752100
18
C 5.20788600 -0.40151600 0.72746200 C 4.19492200 -2.57942200 0.56741500 C 6.47130800 -0.98222600 0.66955100 H 5.11078200 0.67934100 0.84883800 C 5.45658300 -3.16411200 0.50900700 H 3.30251200 -3.20878100 0.56461600 C 6.59661900 -2.36479200 0.55426600 H 7.35994300 -0.35693800 0.72749500 H 5.55143400 -4.24601100 0.44140300 H 7.58352500 -2.82096500 0.51531400 Cu 0.17657600 0.68342000 -0.29641700 C -1.00587300 0.65344600 2.63880700 N 0.01863200 0.44766800 2.12096000 C -2.28586600 0.92084600 3.25287300 H -2.21077100 0.88977000 4.34454600 H -2.63797800 1.91027300 2.94258700 H -3.02329500 0.18197800 2.91889600 O -1.38403800 1.77560700 -0.27091000 O -2.52120200 1.02895900 0.13420000 C -3.53270200 0.99049000 -0.94014300 C -2.90842300 0.50839700 -2.23723400 H -2.46334200 -0.48823800 -2.13590700 H -3.66099500 0.46732300 -3.03233800 H -2.12570900 1.20642700 -2.54602800 C -4.09004800 2.39678800 -1.11534200 H -4.87023400 2.41156000 -1.88458200 H -4.52486500 2.77367700 -0.18380700 H -3.28502400 3.07405300 -1.41985300 C -4.55046000 0.03291100 -0.34525600 C -4.91744000 -1.16251100 -0.96973300 C -5.11284600 0.32868000 0.90407700 C -5.82202400 -2.03467700 -0.36598700 H -4.50548200 -1.41926200 -1.94405900 C -6.00661400 -0.54480300 1.51426900 H -4.84350400 1.26049500 1.40044600 C -6.36490600 -1.73271800 0.87909900 H -6.10689100 -2.95269500 -0.87722200 H -6.43552500 -0.29260100 2.48268800 H -7.07241100 -2.41317300 1.34870900
3c
Energy: -1729.49282065 a.u.
C -0.05486100 3.27751000 -0.75459200 C -0.63394100 4.35456700 -1.41169000 C -2.02118700 4.40757300 -1.51024000 C -2.78381900 3.38938100 -0.94477000 C -2.13825000 2.34707100 -0.29044100 N -0.79240000 2.29958000 -0.21156600 H -2.50684500 5.23311600 -2.02592800 H 1.02081900 3.16107600 -0.63664800 H -0.00608800 5.13053300 -1.84062700 H -3.87066400 3.40133900 -1.00282500 C -2.86533900 1.23994000 0.42287400 H -2.99816600 1.53334700 1.47287800 H -3.86439500 1.07021800 -0.00586200 N -2.04483600 0.01863600 0.41558600
19
C -2.35517000 -0.91209300 1.51097500 H -3.24049800 -1.52734400 1.29063100 H -2.58851800 -0.30489800 2.39608800 C -1.15276600 -1.76266100 1.82204900 C -1.24426100 -3.03532600 2.37454000 N 0.04160000 -1.18390300 1.58933200 C -0.07376600 -3.70904200 2.71130300 H -2.22127200 -3.48519100 2.54203800 C 1.17139500 -1.82577900 1.91977000 C 1.15429900 -3.09330400 2.48701800 H -0.12122400 -4.70635000 3.14332100 H 2.08801700 -1.28397000 1.69338100 H 2.08841500 -3.58857900 2.73843600 C -2.02375900 -0.65855700 -0.92647800 H -1.27375100 -1.45709400 -0.85332800 H -1.63400500 0.08278600 -1.63644800 C -3.34613400 -1.19828300 -1.38547200 C -4.22057000 -0.39961900 -2.13148500 C -3.73114700 -2.50706200 -1.07253700 C -5.45720800 -0.88972900 -2.54010000 H -3.91434400 0.60937600 -2.41534100 C -4.96722400 -3.00019000 -1.47971000 H -3.04088900 -3.15286100 -0.52594100 C -5.83366500 -2.18965700 -2.20968600 H -6.12321000 -0.26156800 -3.12804200 H -5.25002000 -4.02277200 -1.23851600 H -6.79725100 -2.57656100 -2.53418600 Cu -0.07861300 0.67638800 0.74062200 C 0.17402000 1.63538500 3.52087800 N -0.87427400 1.56208600 3.01191000 C 1.50122400 1.68962200 4.08937300 H 1.76845500 2.71774100 4.35321600 H 1.56491000 1.06797300 4.98813000 H 2.20419500 1.32079100 3.33053900 O 1.74294900 1.16363200 0.95122900 O 2.32537600 0.20650000 -0.00415600 C 3.61163500 0.70222000 -0.46578800 C 3.44332000 2.04337800 -1.15921200 H 3.07848900 2.77672600 -0.43369200 H 4.39871300 2.40987400 -1.55035000 H 2.73064700 1.97489800 -1.99006700 C 4.54879000 0.84425500 0.73157500 H 4.62932700 -0.10051000 1.28188100 H 5.55479100 1.12895600 0.40373800 H 4.17451500 1.61516300 1.41432900 C 4.06812900 -0.41838500 -1.38674000 C 4.13260600 -1.72682400 -0.89035400 C 4.44113000 -0.19431300 -2.71387400 C 4.55777200 -2.77820000 -1.69360200 H 3.84198700 -1.92021800 0.14195300 C 4.87688500 -1.24481800 -3.51898500 H 4.40262900 0.80941000 -3.13193700 C 4.93503600 -2.53930500 -3.01352700 H 4.60147500 -3.78746000 -1.28771800 H 5.17170400 -1.04661700 -4.54779400 H 5.27552000 -3.35896800 -3.64319900
3d
20
Energy: -1729.50175755 a.u.
C -0.69042800 -2.45924800 -1.27012400 C -0.64683600 -3.84761700 -1.29445900 C 0.31813100 -4.49798900 -0.53044600 C 1.20414800 -3.74379800 0.23417900 C 1.09432900 -2.35756700 0.22107800 N 0.15987400 -1.73817300 -0.52688400 H 0.38685900 -5.58375200 -0.53551000 H -1.40921200 -1.87615900 -1.84407800 H -1.34921200 -4.40380500 -1.90938700 H 1.97499800 -4.22161500 0.83661900 C 1.96423800 -1.45467200 1.06010900 H 1.46755300 -1.27876900 2.02333800 H 2.93582300 -1.92610500 1.27486500 N 2.11255600 -0.15241900 0.40018800 C 2.38688100 0.97127500 1.30519000 H 3.43923500 1.00631100 1.62698800 H 1.76822800 0.82382800 2.20082300 C 1.97911600 2.26130100 0.64087700 C 2.60984400 3.47667300 0.88076300 N 0.92816800 2.17567000 -0.20111700 C 2.13983900 4.62127500 0.24277100 H 3.45923900 3.52013100 1.56018700 C 0.48091400 3.27369900 -0.82632600 C 1.05955500 4.52005500 -0.62910800 H 2.61954900 5.58174400 0.41790700 H -0.36326500 3.11335000 -1.49655800 H 0.67252400 5.38875100 -1.15435300 C 3.05861700 -0.20788500 -0.76160800 H 2.96687700 0.75533900 -1.28041400 H 2.66454600 -0.97611700 -1.44004400 C 4.48859800 -0.48854400 -0.40264800 C 4.96796300 -1.80241700 -0.35081100 C 5.36684600 0.55981300 -0.10512400 C 6.28759400 -2.06398700 0.00593000 H 4.30337600 -2.62620500 -0.61929800 C 6.68684900 0.30189500 0.25212100 H 5.01478300 1.59076800 -0.18078300 C 7.14706700 -1.01158600 0.31276100 H 6.64993500 -3.08961800 0.03221000 H 7.36151900 1.12698900 0.47108400 H 8.18062100 -1.21434800 0.58518500 Cu 0.18720700 0.31123100 -0.39813300 C -1.65932500 -0.55278600 2.01413600 N -0.66020900 0.03526300 1.87636000 C -2.88506700 -1.29999200 2.17017500 H -3.20307500 -1.69019200 1.19530500 H -2.74336100 -2.12933800 2.87095900 H -3.68938900 -0.65393000 2.54023700 O -1.31528700 0.68832400 -1.48777700 O -2.47587200 0.12340200 -0.86197500 C -3.50208300 1.15626900 -0.70029000 C -3.00583800 2.23433100 0.24923800 H -2.05220400 2.62336100 -0.11988400 H -3.71111400 3.07110800 0.30419900 H -2.84564200 1.84973400 1.26307000 C -3.83220400 1.74543700 -2.06727000 H -4.12425900 0.95692200 -2.76901300 H -4.66274500 2.45552800 -1.98575200
21
H -2.96008900 2.26543000 -2.47708700 C -4.67575500 0.35960500 -0.15868400 C -5.00973700 -0.86293100 -0.75669500 C -5.44258500 0.80449100 0.92168300 C -6.06276300 -1.63089200 -0.26985000 H -4.42429200 -1.21482100 -1.60496900 C -6.50621800 0.04201600 1.40245400 H -5.21599700 1.75744500 1.39717100 C -6.81347100 -1.18204700 0.81543800 H -6.30490700 -2.58019200 -0.74470900 H -7.09697000 0.40950200 2.23968800 H -7.64168200 -1.77823300 1.19330400
4) – [CuII(bpa)(O2Cm)]+
4a (structure ii in Figure 8)
Energy: -1596.74023326 a.u.
C -1.56188600 -2.19384600 -0.55155500 C -1.68993800 -3.57365500 -0.44945800 C -0.68892500 -4.29320600 0.19439100 C 0.40398400 -3.61402400 0.73014600 C 0.46236400 -2.23237500 0.60591700 N -0.50461400 -1.54683200 -0.03863600 H -0.75544700 -5.37552200 0.28210700 H -2.30583300 -1.56007600 -1.03664400 H -2.56265900 -4.06477900 -0.87112600 H 1.20041000 -4.14733200 1.24624500 C 1.54568700 -1.39146100 1.23524500 H 1.21505500 -1.08664600 2.23876200 H 2.47322700 -1.96826100 1.37189700 N 1.76213900 -0.16783100 0.45119800 C 2.26971300 0.97440900 1.22220000 H 3.35835100 0.92497900 1.37830400 H 1.80503400 0.93315700 2.21808200 C 1.87223700 2.26673100 0.55427800 C 2.64506800 3.41931600 0.61573800 N 0.67804300 2.25550000 -0.07603900 C 2.16751500 4.58607200 0.02386700 H 3.60691900 3.39939100 1.12507300 C 0.21536300 3.37733100 -0.64964400 C 0.93244600 4.56638100 -0.61631600 H 2.75737300 5.49932900 0.05936200 H -0.75956500 3.28740300 -1.12604600 H 0.52746200 5.45556300 -1.09134500 C 2.55641400 -0.42087200 -0.79875500 H 2.51175900 0.50817000 -1.38308100 H 2.00146000 -1.18299600 -1.36219600 C 3.97752200 -0.84513100 -0.57327500 C 4.30858800 -2.19993600 -0.45453100 C 4.99691400 0.10874200 -0.47145000 C 5.62349200 -2.59148200 -0.22045000 H 3.52949900 -2.95530100 -0.57589600 C 6.31250700 -0.27976100 -0.23731200 H 4.75734400 1.16561200 -0.60620200 C 6.62572600 -1.63079700 -0.10596000
22
H 5.86919600 -3.64836700 -0.14103100 H 7.09704800 0.47113700 -0.17126900 H 7.65492100 -1.93628000 0.06969500 Cu -0.16337600 0.43494300 -0.24296600 O -1.77251200 0.73609600 -1.16321700 O -2.51897200 1.86181800 -0.74303600 C -3.33612900 1.52093700 0.42246400 C -4.30916100 2.69077500 0.49604200 H -4.92114100 2.74258600 -0.40988700 H -4.97788200 2.57244000 1.35495100 H -3.76925100 3.63886000 0.60673000 C -2.43749200 1.49605100 1.65260200 H -3.02052900 1.41641400 2.57675600 H -1.74358200 0.64112400 1.63203300 H -1.85608900 2.42399600 1.70494300 C -4.06083200 0.21138500 0.16765700 C -4.21143400 -0.76311300 1.15581400 C -4.60246600 -0.03094900 -1.10065100 C -4.88650300 -1.95442300 0.88614000 H -3.80349300 -0.60352100 2.15292400 C -5.26628100 -1.22075200 -1.37496400 H -4.46932600 0.71454000 -1.88299200 C -5.41162000 -2.18895200 -0.38020700 H -5.00063100 -2.69835900 1.67293200 H -5.67540000 -1.39355700 -2.36876900 H -5.94067400 -3.11661700 -0.59178500
4b
Energy: -1596.73797663 a.u.
C -1.56188600 -2.19384600 -0.55155500 C -1.68993800 -3.57365500 -0.44945800 C -0.68892500 -4.29320600 0.19439100 C 0.40398400 -3.61402400 0.73014600 C 0.46236400 -2.23237500 0.60591700 N -0.50461400 -1.54683200 -0.03863600 H -0.75544700 -5.37552200 0.28210700 H -2.30583300 -1.56007600 -1.03664400 H -2.56265900 -4.06477900 -0.87112600 H 1.20041000 -4.14733200 1.24624500 C 1.54568700 -1.39146100 1.23524500 H 1.21505500 -1.08664600 2.23876200 H 2.47322700 -1.96826100 1.37189700 N 1.76213900 -0.16783100 0.45119800 C 2.26971300 0.97440900 1.22220000 H 3.35835100 0.92497900 1.37830400 H 1.80503400 0.93315700 2.21808200 C 1.87223700 2.26673100 0.55427800 C 2.64506800 3.41931600 0.61573800 N 0.67804300 2.25550000 -0.07603900 C 2.16751500 4.58607200 0.02386700 H 3.60691900 3.39939100 1.12507300 C 0.21536300 3.37733100 -0.64964400 C 0.93244600 4.56638100 -0.61631600 H 2.75737300 5.49932900 0.05936200 H -0.75956500 3.28740300 -1.12604600 H 0.52746200 5.45556300 -1.09134500
23
C 2.55641400 -0.42087200 -0.79875500 H 2.51175900 0.50817000 -1.38308100 H 2.00146000 -1.18299600 -1.36219600 C 3.97752200 -0.84513100 -0.57327500 C 4.30858800 -2.19993600 -0.45453100 C 4.99691400 0.10874200 -0.47145000 C 5.62349200 -2.59148200 -0.22045000 H 3.52949900 -2.95530100 -0.57589600 C 6.31250700 -0.27976100 -0.23731200 H 4.75734400 1.16561200 -0.60620200 C 6.62572600 -1.63079700 -0.10596000 H 5.86919600 -3.64836700 -0.14103100 H 7.09704800 0.47113700 -0.17126900 H 7.65492100 -1.93628000 0.06969500 Cu -0.16337600 0.43494300 -0.24296600 O -1.77251200 0.73609600 -1.16321700 O -2.51897200 1.86181800 -0.74303600 C -3.33612900 1.52093700 0.42246400 C -4.30916100 2.69077500 0.49604200 H -4.92114100 2.74258600 -0.40988700 H -4.97788200 2.57244000 1.35495100 H -3.76925100 3.63886000 0.60673000 C -2.43749200 1.49605100 1.65260200 H -3.02052900 1.41641400 2.57675600 H -1.74358200 0.64112400 1.63203300 H -1.85608900 2.42399600 1.70494300 C -4.06083200 0.21138500 0.16765700 C -4.21143400 -0.76311300 1.15581400 C -4.60246600 -0.03094900 -1.10065100 C -4.88650300 -1.95442300 0.88614000 H -3.80349300 -0.60352100 2.15292400 C -5.26628100 -1.22075200 -1.37496400 H -4.46932600 0.71454000 -1.88299200 C -5.41162000 -2.18895200 -0.38020700 H -5.00063100 -2.69835900 1.67293200 H -5.67540000 -1.39355700 -2.36876900 H -5.94067400 -3.11661700 -0.59178500
4c
Energy: -1596.75394445 a.u.
C -2.08450800 2.10558300 0.09453400 C -3.19448000 2.71383500 0.66428000 C -3.78596100 2.11973000 1.77524700 C -3.25942600 0.93106300 2.26867500 C -2.14896400 0.37414800 1.64398200 N -1.56817100 0.96768900 0.58484000 H -4.65638900 2.57077700 2.24675400 H -1.56713100 2.51597600 -0.76993700 H -3.58503500 3.63437100 0.23948700 H -3.70807000 0.43009400 3.12487100 C -1.50157100 -0.89570600 2.14449800 H -0.78234800 -0.63340800 2.93383500 H -2.25493300 -1.54978200 2.61457600 N -0.76156900 -1.59933200 1.08579100 C 0.43685900 -2.31324800 1.55248400 H 0.19096200 -3.30386500 1.96845700 H 0.89057400 -1.72431900 2.36178100 C 1.44028300 -2.43533100 0.43214900
24
C 2.40667000 -3.43446100 0.38701200 N 1.37752900 -1.48206600 -0.51635000 C 3.32328700 -3.44001900 -0.66019700 H 2.43467100 -4.19837700 1.16173400 C 2.26169500 -1.48129500 -1.52381300 C 3.25085400 -2.44809300 -1.63462500 H 4.08400900 -4.21558600 -0.71676000 H 2.14335700 -0.66412200 -2.23553100 H 3.94573600 -2.42330300 -2.46960300 C -1.62937300 -2.52468900 0.29075700 H -2.16565400 -3.18828100 0.98981000 H -0.94546900 -3.15104500 -0.29655900 C -2.57530400 -1.80064200 -0.62011500 C -3.88800500 -1.52629300 -0.23280800 C -4.72422700 -0.77458900 -1.05509300 H -4.25849700 -1.90463600 0.72171200 C -2.94808200 -0.57111100 -2.67730500 C -4.25240600 -0.29039800 -2.27358400 H -5.74725400 -0.56979700 -0.74548300 H -2.57709100 -0.20569500 -3.63241500 H -4.90642100 0.29588300 -2.91586400 Cu -0.03086800 -0.06165200 -0.23461100 O 0.51746900 1.05578900 -1.66862600 O 0.66564700 2.39722700 -1.21708500 C 2.06133900 2.65759600 -0.88918900 C 2.02922000 4.10816200 -0.42315900 H 3.03374300 4.43574100 -0.13597000 H 1.67071400 4.75721100 -1.22929800 H 1.36996500 4.23572700 0.44251300 C 2.47010500 1.72796200 0.24488800 C 3.62927500 0.95143500 0.21579300 C 1.64004700 1.63822100 1.37295100 C 3.95163600 0.10362900 1.27647100 H 4.29586100 1.00185100 -0.64365100 C 1.96112200 0.79836900 2.43664100 H 0.74127500 2.25414200 1.41677300 C 3.12027800 0.02195400 2.38938700 H 4.86474300 -0.48830500 1.23405700 H 1.32164900 0.77462900 3.32002600 H 3.38405300 -0.62481400 3.22520000 C 2.90343300 2.51460300 -2.14467200 H 2.49369500 3.15559400 -2.93108500 H 3.94081200 2.81805700 -1.96434900 H 2.89737200 1.48374700 -2.51200700 C -2.11879900 -1.32923700 -1.85686900 H -1.10313700 -1.56578700 -2.18355300
4d
Energy: -1596.74171808 a.u.
C -1.67891100 -2.11462000 -1.40309900 C -2.83474800 -2.85708400 -1.59736200 C -4.05392600 -2.18987300 -1.66607900 C -4.07588200 -0.80378500 -1.55214300 C -2.88091700 -0.12092700 -1.36370100 N -1.70517800 -0.77753000 -1.28317000 H -4.98023600 -2.74245100 -1.80721900 H -0.68812800 -2.56500400 -1.34002400 H -2.77465700 -3.93790600 -1.68971600
25
H -5.01197200 -0.25047500 -1.59848700 C -2.81136300 1.38644500 -1.31552500 H -2.61979700 1.75562900 -2.33280800 H -3.78108300 1.80646700 -1.00588400 N -1.71079900 1.85174600 -0.45383500 C -1.05030600 3.08544100 -0.91905700 H -1.61532800 3.98638400 -0.62964300 H -1.02447700 3.06274500 -2.01770500 C 0.36575500 3.14695100 -0.40412200 C 1.01219800 4.32771600 -0.06505000 N 1.00277000 1.96000300 -0.35127400 C 2.35007800 4.27516500 0.32232300 H 0.47649500 5.27386700 -0.10861400 C 2.29224700 1.90297400 0.01447000 C 3.00197600 3.04675400 0.35821300 H 2.87552100 5.18809300 0.59399500 H 2.73487000 0.90614800 0.00988000 H 4.04545300 2.96401900 0.65023200 C -2.14483700 2.03636300 0.96448000 H -2.81048900 2.91573000 1.00618000 H -1.23847100 2.28601700 1.53352200 C -2.83284700 0.83569000 1.53602200 C -4.22579500 0.79180400 1.63527900 C -4.86509200 -0.35034000 2.11115000 H -4.81385500 1.66375900 1.34410200 C -2.72300100 -1.42151500 2.40894600 C -4.11484400 -1.46090300 2.49015300 H -5.94993000 -0.37057500 2.19271100 H -2.13178300 -2.27928200 2.72568000 H -4.61281900 -2.35259300 2.86540400 Cu -0.14703200 0.36349700 -0.78344100 O 1.41155900 -0.60281700 -1.23412800 O 1.43820500 -2.00527600 -1.07298500 C 2.03625600 -2.33309000 0.21880700 C 2.17887500 -3.84722800 0.14475700 H 2.64486600 -4.22610300 1.06031300 H 1.19961100 -4.32901900 0.03111600 H 2.80916700 -4.13429500 -0.70296900 C 3.38952700 -1.65039800 0.33659300 C 3.87087200 -1.17607800 1.55947900 C 4.18468300 -1.49203500 -0.80436100 C 5.11440000 -0.54956500 1.64166100 H 3.27736700 -1.28938200 2.46575600 C 5.42131200 -0.86199100 -0.72514600 H 3.80887400 -1.84201200 -1.76390200 C 5.89071800 -0.38575500 0.49876400 H 5.47453500 -0.19211400 2.60484700 H 6.02237900 -0.74058300 -1.62444400 H 6.86125500 0.10309100 0.56066300 C 1.06407600 -1.92431500 1.31612500 H 0.05993900 -2.29922800 1.07863900 H 1.34976400 -2.33423900 2.29106800 H 1.02358300 -0.83038900 1.41270300 C -2.08928400 -0.27550800 1.94164500 H -0.99967500 -0.23425600 1.88990400
5) – Self – Decomposition Structures (Bpa)
5a (structure iii in Figure 8)
26
Energy: -1596.69181842 a.u.
C 0.17641400 2.97542500 -1.61467200 C -0.19753100 4.30801400 -1.50748800 C -1.14596200 4.65953900 -0.55122400 C -1.68696400 3.67197700 0.26799000 C -1.25952100 2.35934200 0.11072000 N -0.34795100 2.02721400 -0.82637100 H -1.46337800 5.69428200 -0.44352000 H 0.92239300 2.63349400 -2.33017000 H 0.24738100 5.05120800 -2.16313200 H -2.42820000 3.91416600 1.02744200 C -1.71016800 1.22610200 0.99758000 H -1.01696700 1.14260400 1.84835100 H -2.71246100 1.41044700 1.41353200 N -1.64015900 -0.03815000 0.25091400 C -1.52779800 -1.24169100 1.09132000 H -2.49401400 -1.53099100 1.53121300 H -0.84941100 -0.99808400 1.92216700 C -0.92001200 -2.36150200 0.28510200 C -1.15688700 -3.70781400 0.53333100 N -0.06299400 -1.96745900 -0.67521900 C -0.46970200 -4.65876600 -0.21770000 H -1.86078100 -4.00426900 1.30901800 C 0.60939100 -2.87575400 -1.39049400 C 0.43247000 -4.23942600 -1.19096900 H -0.63655900 -5.71904200 -0.04108200 H 1.30638000 -2.46702400 -2.12118100 H 0.99051400 -4.95419600 -1.78936100 C -2.73192600 -0.15679900 -0.77574800 H -2.49015200 -1.04410400 -1.37407900 H -2.62706700 0.71471200 -1.43431300 C -4.11883600 -0.24543100 -0.21139100 C -4.87121000 0.91209200 0.01931000 C -4.68199100 -1.48843000 0.09990800 C -6.14951400 0.83115500 0.56366600 H -4.45826000 1.88449700 -0.25731300 C -5.95993500 -1.57249200 0.64423800 H -4.11941900 -2.39996900 -0.11221000 C -6.69280100 -0.41166100 0.88127300 H -6.72818300 1.73769400 0.72811000 H -6.39024300 -2.54545600 0.87190900 H -7.69464800 -0.47659000 1.30020700 Cu 0.19549600 0.07221000 -0.74237400 O 1.85903800 0.10246000 -1.47476700 O 1.76476000 -0.20343600 0.73369300 C 2.80765400 0.58411400 1.18673700 C 2.55645200 2.06653800 0.90908700 H 1.58317800 2.37055000 1.31743000 H 3.32684500 2.69981600 1.36107800 H 2.56000600 2.22810300 -0.17369900 C 2.74807300 0.32641400 2.72489300 H 2.88890100 -0.73600100 2.94225000 H 3.55365700 0.89434600 3.20256500 H 1.78662200 0.66046100 3.13066700 C 4.15972900 0.12042300 0.66591400 C 5.32461600 0.81398200 1.01258500 C 4.26592400 -1.01605100 -0.13847700 C 6.56593400 0.39681900 0.54484100 H 5.26720400 1.69222100 1.65689000
27
C 5.50747700 -1.43248200 -0.60976100 H 3.36212800 -1.55840200 -0.40456200 C 6.66064800 -0.72900900 -0.27077200 H 7.46152100 0.95077000 0.81942600 H 5.57576300 -2.31250100 -1.24706700 H 7.63103700 -1.05803400 -0.63719500
5b
Energy: -1596.69531235 a.u.
C 0.11300200 3.28784700 -1.87075700 C -0.18058900 4.57587800 -1.44374800 C -0.79441900 4.74407900 -0.20592600 C -1.08861800 3.62349600 0.56655800 C -0.75646400 2.36478800 0.08061000 N -0.17491700 2.21091400 -1.12761500 H -1.04223800 5.73931500 0.15632700 H 0.60505400 3.08764000 -2.82080900 H 0.06715900 5.42619600 -2.07285100 H -1.56388100 3.72034000 1.54108100 C -0.93415200 1.09510900 0.87310300 H -0.00655300 0.89520700 1.43368900 H -1.74824900 1.18631200 1.60841900 N -1.13357500 -0.03362300 -0.04662100 C -0.79310800 -1.34924900 0.52033000 H -1.58557500 -1.73193600 1.18092900 H 0.11287700 -1.21717600 1.13122900 C -0.47975600 -2.31126100 -0.59675800 C -0.65437800 -3.68638600 -0.49948000 N 0.05458900 -1.74967900 -1.69757500 C -0.24295500 -4.49144200 -1.55909100 H -1.09758300 -4.11757100 0.39649200 C 0.46894400 -2.51959800 -2.70940300 C 0.33456500 -3.90224200 -2.67978900 H -0.36933000 -5.57064600 -1.50692200 H 0.93018200 -1.98849400 -3.54020900 H 0.67617000 -4.50034800 -3.52002500 C -2.48713400 -0.01868700 -0.69471900 H -2.46443200 -0.80300700 -1.46169900 H -2.56524100 0.94247800 -1.21880800 C -3.63789100 -0.21457400 0.24767500 C -4.24712400 0.88325800 0.86609900 C -4.11697800 -1.49870400 0.53090900 C -5.29953600 0.70217600 1.75853800 H -3.90728200 1.89217500 0.62267800 C -5.16930200 -1.68306600 1.42279400 H -3.67459100 -2.35933600 0.02509300 C -5.75834400 -0.58245300 2.04116500 H -5.77164500 1.56481000 2.22412200 H -5.53946100 -2.68577500 1.62603300 H -6.58584200 -0.72490100 2.73285500 Cu 0.34757700 0.28055000 -1.48887000 O 1.83809200 0.43601100 -2.52506300 O 2.12648400 -0.22972100 -0.40714800 C 3.23442300 0.49933600 0.05769800 C 2.98500000 2.00002200 0.01080100 H 2.05835400 2.27750200 0.52830600 H 3.81450000 2.55736100 0.46156200 H 2.89050500 2.29487400 -1.03941000
28
C 4.48799100 0.14775300 -0.73170300 H 5.36984900 0.65113200 -0.31916100 H 4.67474300 -0.93005400 -0.73364500 H 4.35044900 0.46732500 -1.77032900 C 3.22086200 -0.08574200 1.47837500 C 2.90415700 0.68476100 2.60578200 C 3.44382300 -1.46440800 1.64216300 C 2.87272800 0.10275100 3.86859000 H 2.73026400 1.75414800 2.50730100 C 3.39867900 -2.04507500 2.90335500 H 3.65325200 -2.07703100 0.76793000 C 3.11449500 -1.26273400 4.02160800 H 2.66840100 0.72028300 4.74119700 H 3.58865600 -3.11056300 3.01606400 H 3.08496500 -1.71360800 5.01149700
5c
Energy: -1596.69438272 a.u.
C -1.25177800 -2.10463000 -2.47963200 C -1.23977000 -3.48966600 -2.57873200 C -0.56423700 -4.22211600 -1.60585200 C 0.06404400 -3.55101900 -0.56034600 C -0.00011900 -2.16406900 -0.51690100 N -0.63569800 -1.46289600 -1.47823200 H -0.52824900 -5.30796600 -1.66005200 H -1.76418500 -1.47243400 -3.20332600 H -1.74524800 -3.97874400 -3.40676300 H 0.58954000 -4.09306300 0.22389700 C 0.56895200 -1.32605600 0.59572200 H -0.23147000 -1.11198300 1.32274000 H 1.37500700 -1.84872500 1.13210500 N 1.01800000 -0.04375800 0.02683300 C 1.14761000 1.06010300 0.99043100 H 2.04371200 0.95696900 1.62093800 H 0.26691100 1.01628300 1.64946900 C 1.13714700 2.36811300 0.23845700 C 1.75071500 3.52409800 0.70462300 N 0.44256000 2.35689000 -0.91538000 C 1.61729700 4.69866200 -0.03250000 H 2.31777200 3.50406700 1.63383200 C 0.30071100 3.48525500 -1.61719200 C 0.87689700 4.68294800 -1.21006700 H 2.08661600 5.61735800 0.31242900 H -0.30286300 3.40588900 -2.51960300 H 0.74568000 5.58079800 -1.80764700 C 2.24649000 -0.20651900 -0.82596100 H 2.40047200 0.75435000 -1.33006300 H 1.98703400 -0.93854200 -1.60066700 C 3.47362900 -0.62907700 -0.07376100 C 3.78098500 -1.98511000 0.08495400 C 4.32910600 0.32602800 0.48743700 C 4.90779600 -2.37908100 0.80035300 H 3.14128000 -2.73731600 -0.38157900 C 5.45641800 -0.06475200 1.20364500 H 4.11896000 1.38715100 0.33795800 C 5.74390400 -1.41838000 1.36478500 H 5.14152700 -3.43631900 0.90713900 H 6.11926500 0.68761900 1.62593600
29
H 6.62875400 -1.72467000 1.91855100 Cu -0.60480700 0.54098200 -1.13184500 O -2.08513300 1.04845000 -2.02633200 O -1.89906100 1.70511900 0.19926300 C -3.02414100 1.32464400 0.93512200 C -4.30324800 1.59434800 0.13970200 H -5.18925500 1.32808200 0.72710600 H -4.35695200 2.65537900 -0.12352200 H -4.30185900 1.02432600 -0.79266100 C -2.89977700 -0.13176200 1.37529900 C -2.50434400 -0.50536200 2.66554600 C -3.13628300 -1.14513000 0.43659500 C -2.34664900 -1.84843000 3.00681700 H -2.33086500 0.25234500 3.42746800 C -2.98844200 -2.48604300 0.77769100 H -3.43319500 -0.87389500 -0.57630400 C -2.58571400 -2.84427400 2.06291000 H -2.04950100 -2.11533400 4.01947700 H -3.19004300 -3.25636300 0.03353400 H -2.47644100 -3.89338100 2.33240500 C -2.97461800 2.31587600 2.12304400 H -3.79698700 2.08650900 2.81108300 H -2.02707900 2.25464500 2.66801800 H -3.09492600 3.33668400 1.75247600
5d (structure iv in Figure 8)
Energy: -1729.45013694 a.u.
C -0.17785200 2.98304400 1.29248000 C 0.22532300 4.30986000 1.22153600 C 1.21524800 4.65559400 0.30576400 C 1.76603600 3.66896100 -0.50748300 C 1.30351800 2.36356200 -0.38523900 N 0.35003800 2.03820600 0.50725800 H 1.55794000 5.68490900 0.22628300 H -0.95557800 2.64205700 1.97534500 H -0.22734200 5.05356700 1.87153900 H 2.54196700 3.90560800 -1.23341800 C 1.76312500 1.23067900 -1.26459500 H 1.07961700 1.15195900 -2.12339100 H 2.77131400 1.41177200 -1.66759400 N 1.67975400 -0.03852400 -0.52483700 C 1.58841200 -1.22365700 -1.39550500 H 2.56617600 -1.50416400 -1.81519800 H 0.93485800 -0.95850000 -2.23939100 C 0.95476100 -2.36214900 -0.64004800 C 1.23013600 -3.70277900 -0.88326900 N 0.03650300 -1.99054100 0.26885100 C 0.51871800 -4.67086400 -0.17881000 H 1.98410800 -3.98085300 -1.61762600 C -0.65272600 -2.91488100 0.94368500 C -0.44293800 -4.27418300 0.74619400 H 0.71403300 -5.72688500 -0.35212400 H -1.39306900 -2.52053200 1.64009800 H -1.02000900 -5.00369800 1.30785300 C 2.76013600 -0.17072200 0.51389700 H 2.50691000 -1.06220500 1.10022200 H 2.63805400 0.68452800 1.18926100 C 4.15310600 -0.24869500 -0.03614300
30
C 4.90596400 0.91284200 -0.24473400 C 4.72536600 -1.48577500 -0.35465200 C 6.19115500 0.84221500 -0.77421400 H 4.48596800 1.88052700 0.03769400 C 6.01022200 -1.56036800 -0.88410000 H 4.16263300 -2.40100800 -0.15944700 C 6.74257900 -0.39503900 -1.09935600 H 6.76878200 1.75248900 -0.92164800 H 6.44613700 -2.52958800 -1.11762600 H 7.74958800 -0.45219400 -1.50711600 Cu -0.16479800 0.04910600 0.46614900 O -1.88122900 0.10154300 1.10818200 O -1.70947700 -0.06522500 -1.13345800 C -2.77188100 0.71491300 -1.54979400 C -2.56602000 2.18413500 -1.17988500 H -1.60076100 2.53919900 -1.56377800 H -3.35263400 2.82229300 -1.59587100 H -2.57495600 2.27702000 -0.08913700 C -2.69211000 0.55434000 -3.09923600 H -2.80126100 -0.49627500 -3.38286600 H -3.51008400 1.12777100 -3.54891700 H -1.73720300 0.93884300 -3.47449100 C -4.11395100 0.17450000 -1.07357400 C -5.29644100 0.87274200 -1.33965400 C -4.19074400 -1.04549100 -0.39878400 C -6.52615300 0.37573100 -0.92003300 H -5.26381200 1.81720600 -1.88392500 C -5.42035900 -1.54338100 0.02241700 H -3.27211700 -1.59065400 -0.19633900 C -6.59169400 -0.83536700 -0.23480600 H -7.43582600 0.93441500 -1.13222000 H -5.46529000 -2.49269200 0.55418600 H -7.55298600 -1.22738900 0.09182200 C -0.22933000 -0.12747800 3.76278800 N 0.54995300 -0.12756800 2.89526500 C -1.22750400 -0.13863800 4.80899600 H -1.10661500 -1.01834300 5.44918000 H -1.14485300 0.75671400 5.43332900 H -2.22723900 -0.16344000 4.36035700
5e (structure v in Figure 8)
Energy: -1729.44511464 a.u.
31
C 1.49248100 3.53083300 0.27680900 C 2.46521600 4.44286400 -0.10675700 C 3.48236600 4.01419700 -0.95441900 C 3.48850000 2.69421900 -1.39569600 C 2.47332000 1.83913300 -0.98398500 N 1.49737200 2.26204400 -0.15372500 H 4.26698200 4.69982500 -1.26621100 H 0.67781800 3.80166900 0.94806300 H 2.42641500 5.46403400 0.26141200 H 4.27029400 2.32548100 -2.05702400 C 2.34497200 0.41799200 -1.46190000 H 1.70939500 0.40220300 -2.35939700 H 3.32153500 0.00306700 -1.75561900 N 1.68535800 -0.39931500 -0.43508700 C 0.98029000 -1.57643000 -0.95823200 H 1.66328900 -2.42294000 -1.12858800 H 0.56398700 -1.30648400 -1.93974100 C -0.14447700 -1.95789100 -0.03327000 C -0.64203700 -3.25269600 0.05236400 N -0.68787700 -0.94777100 0.67765700 C -1.73138500 -3.50463500 0.88111600 H -0.17989400 -4.04799500 -0.52959100 C -1.72528700 -1.19341400 1.49158300 C -2.27952800 -2.45933100 1.61650500 H -2.14253600 -4.50895100 0.95685300 H -2.11037800 -0.33850800 2.04075600 H -3.12890900 -2.61314100 2.27594400 C 2.59556700 -0.73225700 0.71953000 H 1.95787300 -1.18757700 1.48731100 H 2.92975000 0.22852800 1.13082200 C 3.75378500 -1.61525800 0.36356800 C 4.97101000 -1.06282100 -0.05231300 C 3.63804900 -3.00851000 0.43777100 C 6.04054400 -1.88143100 -0.40276200 H 5.08789600 0.02272800 -0.07122300 C 4.70567300 -3.82984700 0.08784500 H 2.70865100 -3.45045300 0.80274100 C 5.90635200 -3.26652600 -0.33844600 H 6.98474100 -1.43867300 -0.71299900 H 4.60597900 -4.91080100 0.16131000 H 6.74390800 -3.90748400 -0.60522700 Cu 0.21621400 0.83767700 0.45336100 C -0.35468800 2.01828300 2.74784200 N 0.47617000 1.18102000 2.56680300 C -1.36358100 2.95993700 2.66223400 H -1.07454500 3.98784300 2.88686100 H -1.53638000 2.63843300 1.07973600 H -2.30872200 2.67429200 3.12768300 O -1.43691600 2.16909700 0.08164100 O -2.56715600 1.23015800 0.15251600 C -3.10912900 1.03472900 -1.18627200 C -1.98931000 0.71493300 -2.16602200 H -1.40580400 -0.15222400 -1.82995100 H -2.39535000 0.48952800 -3.15828100 H -1.31992600 1.57550100 -2.26494500 C -3.85589000 2.28785700 -1.62134300 H -4.30899400 2.14571400 -2.60892200 H -4.65358400 2.53742900 -0.91487400 H -3.16570700 3.13682900 -1.67595300 C -4.03815700 -0.13940900 -0.91483600
32
C -3.92454800 -1.36040000 -1.58449600 C -5.01595000 -0.00996500 0.08102000 C -4.77454800 -2.42107900 -1.27766600 H -3.17834400 -1.49196600 -2.36612400 C -5.85627400 -1.07180500 0.39693900 H -5.10830500 0.93186200 0.61978400 C -5.73929800 -2.28233300 -0.28421500 H -4.68333200 -3.35889800 -1.82332800 H -6.61132400 -0.95108800 1.17152000 H -6.40549600 -3.10994400 -0.04804300
6) – Cyclohexadiene (CHD) Oxidation (Bpa)
6a (structure vi in Figure 8)
Energy: -1830.10369032 a.u.
C -1.03632500 -2.35038000 0.16175800 C -1.01386100 -3.71705900 0.40122200 C 0.15060400 -4.28150500 0.91333700 C 1.24551500 -3.45886900 1.16030600 C 1.14982600 -2.09644500 0.89484200 N 0.01883100 -1.55631400 0.39674100 H 0.20940800 -5.34960700 1.11174700 H -1.92017300 -1.84957800 -0.23671100 H -1.89214200 -4.32067800 0.18556600 H 2.17543200 -3.86522800 1.55525000 C 2.28127100 -1.14116300 1.19797500 H 2.13426800 -0.75072100 2.21613600 H 3.24530300 -1.67775000 1.20080600 N 2.25926200 -0.00705800 0.28557000 C 2.80038400 1.24202700 0.80277100 H 3.89596900 1.31763600 0.69580100 H 2.59114400 1.27063900 1.88250800 C 2.12645800 2.42744300 0.14977500 C 2.79799000 3.62250300 -0.08365700 N 0.81938000 2.28377600 -0.15713200 C 2.10601300 4.69802600 -0.63263400 H 3.85461700 3.70318600 0.16713600 C 0.15255800 3.32135800 -0.68891100 C 0.75744500 4.54583000 -0.93930900 H 2.61528700 5.64032400 -0.82260500 H -0.89934300 3.13760100 -0.90361800 H 0.17970700 5.35868200 -1.37095800 C 2.73730200 -0.33641200 -1.08314900 H 2.50121900 0.53289700 -1.71301700 H 2.11184500 -1.16670300 -1.43995600 C 4.19485800 -0.68657200 -1.17496300 C 4.62022200 -2.01092300 -1.01962300 C 5.15756200 0.30637100 -1.38991300 C 5.97339600 -2.33376300 -1.06181700 H 3.87629900 -2.79986300 -0.89003400 C 6.51178800 -0.01261400 -1.43237300 H 4.83604100 1.33714900 -1.55332300 C 6.92150400 -1.33319000 -1.26312200 H 6.28863200 -3.36929300 -0.95004800 H 7.24846500 0.76820800 -1.61073200 H 7.97923200 -1.58476100 -1.30285800 Cu 0.02585300 0.44174300 0.11321200
33
O -1.85687000 0.67356700 -0.71305400 O -2.65654500 1.67663400 -0.02979200 C -3.32829600 1.05687400 1.10338700 C -4.33190300 0.03227700 0.60605600 H -3.83786300 -0.79836800 0.08514300 H -4.92382700 -0.37881700 1.43148000 H -5.01795200 0.51018600 -0.10054900 C -4.04055400 2.24786300 1.73645000 H -4.59527900 1.92209500 2.62252900 H -3.32750200 3.01918200 2.04619600 H -4.74808000 2.69125900 1.02760900 C -2.27713000 0.49100800 2.04853200 C -2.37821700 -0.77320300 2.63147500 C -1.15580200 1.27754000 2.35737900 C -1.38718400 -1.24750900 3.49169600 H -3.23522600 -1.40772800 2.41146600 C -0.16466300 0.80744400 3.21872400 H -1.08107200 2.27940800 1.93409700 C -0.27711500 -0.46199500 3.78706700 H -1.48823100 -2.23724400 3.93448100 H 0.68112100 1.44902300 3.46780100 H 0.48714000 -0.82765600 4.47146500 C -4.34623900 0.50019600 -2.96849900 C -5.49694200 -0.15707400 -2.69303200 C -4.18751100 -2.26174500 -2.38443600 C -3.05971800 -1.57884100 -2.68890400 H -4.38253100 1.54995200 -3.25867500 H -6.45263600 0.36049500 -2.76604900 H -4.15071300 -3.34073500 -2.23363300 H -2.11346900 -2.11553500 -2.77800200 C -5.52428500 -1.59900000 -2.30500800 H -5.94578500 -1.70820800 -1.28497600 H -6.25451000 -2.14745800 -2.92756000 C -3.05343200 -0.14211100 -2.87749200 H -2.25968100 0.26527100 -3.51232500 H -2.46297600 0.34943000 -1.66366800
6b
Energy: -1830.09259931 a.u.
C 0.23792100 2.77218300 -1.29844000 C 0.72030600 4.04813200 -1.55530100 C 2.07916100 4.20861300 -1.80560100 C 2.90094300 3.08486100 -1.79354400 C 2.34709200 1.83575700 -1.53785400 N 1.02711800 1.68503200 -1.28802500 H 2.49605300 5.19388200 -2.00205200 H -0.81398900 2.59027800 -1.07706200 H 0.03750900 4.89444700 -1.55142800 H 3.96964300 3.16899600 -1.98433200 C 3.16414300 0.56794300 -1.58864900 H 3.02492500 0.10960300 -2.57819900 H 4.23915400 0.79484900 -1.49975500 N 2.70046200 -0.39222700 -0.58963300 C 2.85723400 -1.79615000 -0.96294100 H 3.86023000 -2.19244800 -0.73425900 H 2.73807900 -1.86155000 -2.05404500 C 1.79294900 -2.64878400 -0.31753200 C 2.05134500 -3.94855300 0.09986800
34
N 0.55761800 -2.10402000 -0.21974500 C 1.01553600 -4.71963200 0.61944600 H 3.05999800 -4.34891500 0.01039200 C -0.44033400 -2.84991500 0.28993800 C -0.25315900 -4.15922200 0.71337900 H 1.20019300 -5.73923700 0.95059500 H -1.40683900 -2.35166300 0.35827900 H -1.09319600 -4.71965500 1.11454500 C 3.18067300 -0.08821200 0.78813500 H 2.62354400 -0.75389700 1.46258100 H 2.85430800 0.93843200 1.00804400 C 4.66048300 -0.23447000 0.99669900 C 5.52378800 0.84573900 0.78041800 C 5.20633600 -1.46122400 1.39207600 C 6.89910200 0.69997700 0.93682200 H 5.10685800 1.81910400 0.51327900 C 6.58099700 -1.61072600 1.54969200 H 4.53947700 -2.29947100 1.60443100 C 7.42958200 -0.53086900 1.31647900 H 7.55752600 1.55109800 0.77518200 H 6.99054700 -2.56749500 1.86739700 H 8.50383800 -0.64450100 1.44552400 Cu 0.46830700 -0.12008500 -0.54591100 O -1.24430200 0.61808000 0.26666700 O -2.33429900 -0.33542100 0.33355400 C -3.17590900 -0.21662800 -0.86465200 C -2.33460400 -0.49140200 -2.10039100 H -1.81983300 -1.45834300 -2.03310400 H -2.95249100 -0.49477600 -3.00529100 H -1.58128700 0.29678500 -2.22457900 C -3.79296500 1.17294500 -0.93183700 H -4.41156100 1.27059300 -1.83101300 H -4.42226900 1.36399300 -0.05758100 H -3.01133600 1.94320000 -0.96583900 C -4.22098300 -1.28005800 -0.57282100 C -4.46560900 -2.35360900 -1.43259500 C -4.96064300 -1.18697800 0.61395700 C -5.44018400 -3.30069300 -1.12398400 H -3.90619900 -2.45329000 -2.36087100 C -5.92453100 -2.13741300 0.92745100 H -4.76520200 -0.36218900 1.29942100 C -6.17046400 -3.19664000 0.05564700 H -5.62775800 -4.12294700 -1.81194700 H -6.48919100 -2.05064700 1.85388200 H -6.93080400 -3.93742700 0.29515500 C -3.12816400 1.93763800 2.57969400 C -4.26649900 2.60463300 2.27420100 C -2.90216100 4.34371900 1.11008700 C -1.78361400 3.66268200 1.44640200 H -3.17746600 1.03730600 3.19203800 H -5.22618500 2.24588800 2.64569400 H -2.82723700 5.30747100 0.60707400 H -0.80502600 4.08494000 1.21316300 C -4.26926200 3.85326900 1.45565000 H -4.86433600 3.70205200 0.53280800 H -4.83344800 4.64800400 1.97712400 C -1.83294700 2.36839000 2.09817400 H -0.96990000 2.09924800 2.71711500 H -1.52816500 1.42616900 1.09067200
35
6c
Energy: -1830.09266567 a.u.
C 0.18392300 2.55821900 1.41913600 C -0.13369700 3.87516000 1.72469400 C -1.45357100 4.19289200 2.02474900 C -2.40776500 3.17967900 2.00929000 C -2.02041100 1.88094800 1.70094300 N -0.73683200 1.57699900 1.40409200 H -1.74015600 5.21524600 2.26180800 H 1.19759900 2.24936200 1.16599200 H 0.64633600 4.63177400 1.71834900 H -3.45243900 3.38761600 2.23548400 C -3.00127500 0.73221300 1.72438600 H -2.92780600 0.22684200 2.69831900 H -4.03469200 1.10994300 1.64576700 N -2.66962400 -0.24445400 0.69478500 C -3.06794400 -1.61875200 0.97045700 H -4.11466600 -1.82986400 0.69373400 H -2.99596900 -1.77580400 2.05649400 C -2.13731400 -2.58855700 0.28004400 C -2.57391100 -3.81937800 -0.19771100 N -0.84369400 -2.21407300 0.18350900 C -1.65708800 -4.69304900 -0.77525400 H -3.62619400 -4.08583700 -0.11187100 C 0.03604800 -3.05340500 -0.38635900 C -0.32493700 -4.30299600 -0.87058800 H -1.98104100 -5.66076200 -1.15198500 H 1.06339100 -2.69102000 -0.44126200 H 0.42757100 -4.94780600 -1.31807700 C -3.01189400 0.20618600 -0.68116000 H -2.54152200 -0.51055800 -1.36999000 H -2.50225900 1.16943000 -0.82836800 C -4.48257800 0.32972600 -0.95717200 C -5.15863200 1.52796300 -0.69980300 C -5.21095400 -0.76018700 -1.44740800 C -6.53060000 1.63009300 -0.91032500 H -4.59448900 2.39693800 -0.35455900 C -6.58302700 -0.66165800 -1.65933000 H -4.68788500 -1.68787600 -1.68921800 C -7.24536800 0.53283900 -1.38543700 H -7.04175200 2.57071500 -0.71512600 H -7.13498500 -1.51406800 -2.05032500 H -8.31681900 0.61316200 -1.55614500 Cu -0.39973100 -0.32232800 0.79391600 O 1.62919800 -0.62601900 0.72442000 O 2.36002900 0.57080900 0.34669700 C 2.44681100 0.67772900 -1.11481100 C 1.04888900 0.69040600 -1.71510400 H 0.41571200 1.46057800 -1.25471100 H 1.08743800 0.88089000 -2.79362300 H 0.57091100 -0.28877800 -1.57821400 C 3.25264400 -0.48476000 -1.67530700 H 3.28562500 -0.43402700 -2.76958100 H 4.27917400 -0.47103900 -1.29830200 H 2.79664500 -1.44195300 -1.38797800 C 3.18606700 1.99911100 -1.24302100 C 2.65154000 3.10104700 -1.91545800
36
C 4.44233900 2.12730900 -0.63540200 C 3.36452200 4.29534900 -1.99875100 H 1.67662200 3.03397400 -2.39474900 C 5.14907400 3.32162800 -0.70907700 H 4.85900400 1.28079400 -0.08952800 C 4.61321900 4.40953600 -1.39589600 H 2.93985700 5.13892800 -2.53978500 H 6.12324500 3.40410200 -0.23085900 H 5.16913500 5.34273100 -1.46144800 C 4.67821900 -1.51937600 1.49534600 C 5.58150900 -1.85717100 0.54431300 C 4.17386000 -3.83351500 -0.04944100 C 3.30219500 -3.47839700 0.92277100 H 4.87216800 -0.66609900 2.14519100 H 6.50108300 -1.28248700 0.43554100 H 4.03116200 -4.76245700 -0.60103600 H 2.45797200 -4.13068500 1.15226400 C 5.38816200 -3.02430100 -0.36700900 H 5.35490200 -2.68367200 -1.42154300 H 6.28480300 -3.67075000 -0.35206200 C 3.44004100 -2.24578100 1.67098700 H 2.99775100 -2.22542500 2.67241200 H 2.45540200 -1.35265200 1.12604900
6d
Energy: -1830.09259928 a.u.
C 0.23789700 2.77229400 -1.29829200 C 0.72025000 4.04826400 -1.55510900 C 2.07910000 4.20878600 -1.80541500 C 2.90090600 3.08505200 -1.79340800 C 2.34708700 1.83592600 -1.53775700 N 1.02711900 1.68516000 -1.28791900 H 2.49596800 5.19407200 -2.00183100 H -0.81400600 2.59036100 -1.07691500 H 0.03743100 4.89456200 -1.55119700 H 3.96960300 3.16921900 -1.98419900 C 3.16417700 0.56813800 -1.58861300 H 3.02501700 0.10985600 -2.57819800 H 4.23917700 0.79507300 -1.49966200 N 2.70050100 -0.39210800 -0.58966500 C 2.85725700 -1.79600600 -0.96308300 H 3.86029000 -2.19230200 -0.73456000 H 2.73794900 -1.86133400 -2.05417400 C 1.79306600 -2.64868100 -0.31758200 C 2.05152700 -3.94844700 0.09978500 N 0.55773500 -2.10394200 -0.21967800 C 1.01577900 -4.71954800 0.61945300 H 3.06017800 -4.34879200 0.01020900 C -0.44015700 -2.84985600 0.29009100 C -0.25291800 -4.15916300 0.71350700 H 1.20048400 -5.73915200 0.95057700 H -1.40666500 -2.35162200 0.35851500 H -1.09290700 -4.71961800 1.11474400 C 3.18076100 -0.08819800 0.78811300 H 2.62363000 -0.75390700 1.46253400 H 2.85443300 0.93844300 1.00809200 C 4.66057100 -0.23450700 0.99663600 C 5.52389300 0.84571200 0.78046900
37
C 5.20640600 -1.46131200 1.39187800 C 6.89920400 0.69991100 0.93685400 H 5.10697800 1.81911200 0.51343700 C 6.58106400 -1.61085400 1.54947500 H 4.53953200 -2.29957000 1.60414700 C 7.42966600 -0.53098400 1.31637800 H 7.55764200 1.55104000 0.77530700 H 6.99060000 -2.56766200 1.86707700 H 8.50392000 -0.64464600 1.44541100 Cu 0.46837700 -0.11998300 -0.54578600 O -1.24438200 0.61798000 0.26658100 O -2.33435400 -0.33556900 0.33342800 C -3.17592600 -0.21677500 -0.86480000 C -2.33461100 -0.49167300 -2.10050300 H -1.81976700 -1.45856500 -2.03307200 H -2.95250300 -0.49523500 -3.00540000 H -1.58135000 0.29654800 -2.22481100 C -3.79288100 1.17283800 -0.93209000 H -4.41151700 1.27043100 -1.83124400 H -4.42211900 1.36403100 -0.05781900 H -3.01120000 1.94303000 -0.96622500 C -4.22108500 -1.28010600 -0.57291500 C -4.46562300 -2.35383000 -1.43249700 C -4.96088200 -1.18677300 0.61375800 C -5.44026600 -3.30082300 -1.12381600 H -3.90609900 -2.45371500 -2.36068200 C -5.92483900 -2.13711300 0.92732200 H -4.76548600 -0.36186200 1.29908900 C -6.17069600 -3.19650600 0.05569900 H -5.62777600 -4.12321200 -1.81163500 H -6.48961000 -2.05014600 1.85366700 H -6.93108900 -3.93722300 0.29525900 C -3.12844800 1.93737600 2.57956200 C -4.26671700 2.60444600 2.27398600 C -2.90215300 4.34359300 1.11022700 C -1.78367700 3.66248100 1.44663100 H -3.17786600 1.03699200 3.19182200 H -5.22646500 2.24571100 2.64532800 H -2.82712400 5.30739700 0.60732900 H -0.80504000 4.08472500 1.21356700 C -4.26932100 3.85316100 1.45555500 H -4.86427900 3.70206100 0.53261900 H -4.83354400 4.64786600 1.97703400 C -1.83315200 2.36811700 2.09824700 H -0.97020000 2.09886500 2.71727300 H -1.52827500 1.42596700 1.09064700
6e
Energy: -1830.10634117 a.u.
38
C -1.46420400 -1.13221900 2.33856000 C -2.33748800 -1.88316400 3.11088900 C -2.59769700 -3.19791400 2.73331200 C -1.98334000 -3.70393400 1.59478000 C -1.11945300 -2.89104600 0.86539100 N -0.85831300 -1.62643400 1.24389200 H -3.27813100 -3.81811200 3.31290600 H -1.21485600 -0.09881200 2.58096600 H -2.80454200 -1.44201300 3.98727400 H -2.17454200 -4.72258500 1.26010800 C -0.39035700 -3.42747600 -0.35012600 H 0.51914400 -3.93834900 -0.00187400 H -1.00812600 -4.20576100 -0.83242100 N 0.01082000 -2.39023000 -1.29684900 C 1.33155400 -2.55997900 -1.89465900 H 1.32456400 -3.23637400 -2.76782700 H 1.98551800 -3.02239300 -1.14037500 C 1.92908800 -1.22650000 -2.28161000 C 2.81172300 -1.09907400 -3.34927800 N 1.59715700 -0.17052200 -1.51232200 C 3.36492400 0.14584700 -3.63194400 H 3.05567400 -1.97078900 -3.95404300 C 2.12965500 1.02902800 -1.78995000 C 3.01397600 1.23452600 -2.83951300 H 4.05358200 0.26504500 -4.46561100 H 1.82219400 1.83404100 -1.12186400 H 3.41520200 2.22672500 -3.02913500 C -1.02572200 -2.09391900 -2.31590900 H -1.30730400 -3.02345300 -2.84284300 H -0.55746900 -1.42738800 -3.05297000 C -2.21938000 -1.43267900 -1.69114200 C -3.34774300 -2.16702800 -1.32567300 C -4.37284500 -1.57167800 -0.59187600 H -3.41755000 -3.22004600 -1.60485400 C -3.15281000 0.51075700 -0.58091500 C -4.26623500 -0.23848500 -0.20198900 H -5.24886300 -2.15435200 -0.31306700 H -3.04959800 1.54967100 -0.26973500 H -5.05539300 0.21995700 0.39149500 Cu 0.31848200 -0.53299500 0.02129100 O 0.14478900 1.44195400 0.65136400 O 0.34118300 1.58740400 2.08375200 C 1.75539200 1.81175900 2.36042100 C -2.27363100 3.59097100 -2.13009700 C -3.08958700 4.20582300 0.14816000 C -1.81660600 4.13849100 0.60452900 C -1.01274100 3.53410600 -1.64203000 H -2.45851600 3.40620400 -3.18773400 H -3.89537800 4.49070100 0.82355600 H -1.60725000 4.36606900 1.65045700 H -0.18868800 3.31002600 -2.32252000 C -0.71085300 3.74733800 -0.24210300 H -0.29570400 2.45585900 0.28381200 H 0.26118600 4.19963000 -0.01590800 C -3.44481700 3.96264800 -1.28225300 H -3.94249900 4.85745500 -1.70301100 H -4.23511000 3.19115300 -1.36143100 C 1.77324400 1.81853900 3.88536100 H 2.79507700 1.97411400 4.24626400 H 1.14187200 2.62539100 4.27296700
39
H 1.41026300 0.86840400 4.29152400 C 2.56227600 0.64711700 1.80337000 C 3.70062800 0.81679600 1.01316600 C 2.13959300 -0.66034300 2.08308400 C 4.39004100 -0.28404400 0.50329700 H 4.06135600 1.81784400 0.78183100 C 2.82250300 -1.76288200 1.57337200 H 1.26838700 -0.81030400 2.72015900 C 3.95142400 -1.57644600 0.77522200 H 5.27562100 -0.12641700 -0.11045000 H 2.48030700 -2.76857300 1.81957600 H 4.49695800 -2.43426500 0.38449100 C 2.17419700 3.16585900 1.81521100 H 1.49139200 3.93828400 2.18539200 H 3.18715000 3.42851400 2.13977600 H 2.15489300 3.18246100 0.71939200 C -2.14832400 -0.07978600 -1.33992500 H -1.29051500 0.51866700 -1.65848000
6f
Energy: -1962.85346300 a.u.
C 0.05282200 2.52030200 1.57255400 C -0.33197900 3.73770100 2.12069200 C -1.65318400 3.90306900 2.52187800 C -2.54178300 2.84455100 2.35748900 C -2.08616000 1.65157600 1.80768600 N -0.80215100 1.49549200 1.41692800 H -1.99128700 4.84466700 2.94941900 H 1.07095000 2.33208200 1.23173100 H 0.39585700 4.53855900 2.22058800 H -3.58662200 2.93596900 2.65084100 C -2.98852500 0.45302800 1.63488900 H -2.83942300 -0.23044500 2.48410100 H -4.04722900 0.76428600 1.65296900 N -2.62169000 -0.27444700 0.42712400 C -2.98597500 -1.68327200 0.39349300 H -4.03439300 -1.85495500 0.09462200 H -2.87732400 -2.07485700 1.41565200 C -2.04794700 -2.44232600 -0.51599300 C -2.45429700 -3.56176900 -1.23536200 N -0.77618100 -1.99481000 -0.56738900 C -1.52429600 -4.24941100 -2.00973000 H -3.49218800 -3.88753800 -1.18294300 C 0.11492100 -2.65441000 -1.32066800 C -0.21175600 -3.78904700 -2.05156600 H -1.82291400 -5.12847400 -2.57694500 H 1.12721000 -2.24686100 -1.31277100 H 0.54887100 -4.29019000 -2.64528500 C -2.95238100 0.44999500 -0.82698800 H -2.45900400 -0.09647600 -1.64305400 H -2.46111700 1.43062500 -0.76028400 C -4.42279000 0.60311600 -1.09192400 C -5.12549500 1.70490800 -0.59106100 C -5.12479500 -0.36835000 -1.81416800 C -6.49693700 1.82694500 -0.79415500 H -4.58151600 2.48644500 -0.05620200 C -6.49640800 -0.24983900 -2.01961400 H -4.58112000 -1.21422200 -2.24038300
40
C -7.18509500 0.84638600 -1.50528100 H -7.02859200 2.69419300 -0.40734300 H -7.02752800 -1.00776500 -2.59215100 H -8.25612600 0.94354500 -1.67033800 Cu -0.37755800 -0.37425100 0.67158000 O 1.64934900 -0.44844700 0.41035300 O 2.33020600 0.81627200 0.18814900 C 2.40843200 1.10095900 -1.24796600 C 1.00699500 1.14795000 -1.83680200 H 0.36102900 1.84356600 -1.28591400 H 1.03368800 1.45954600 -2.88720000 H 0.55034300 0.15132700 -1.80068800 C 3.24444500 0.03644400 -1.94491000 H 3.27497000 0.22172600 -3.02471500 H 4.27115100 0.02639500 -1.56710000 H 2.81294000 -0.95963300 -1.77698800 C 3.11565100 2.44603400 -1.22437200 C 2.55682600 3.60012600 -1.77872500 C 4.36930600 2.53843900 -0.60493100 C 3.24223600 4.81246500 -1.73448200 H 1.58343600 3.56090000 -2.26376300 C 5.04866600 3.74951300 -0.55066100 H 4.80679000 1.64891300 -0.15204400 C 4.48808000 4.89127800 -1.12038300 H 2.79785100 5.69849100 -2.18417300 H 6.02120700 3.80300500 -0.06483200 H 5.02255900 5.83865800 -1.08641800 C 4.73268600 -1.54394100 0.97417400 C 5.53312300 -1.84933400 -0.07344000 C 3.91126400 -3.62268600 -0.75649700 C 3.14814200 -3.30708900 0.31470100 H 5.04995800 -0.78776900 1.69243300 H 6.49115700 -1.34458600 -0.19458300 H 3.64114500 -4.46630900 -1.39180800 H 2.25403200 -3.89763800 0.52976100 C 5.16547500 -2.88035400 -1.09100900 H 5.07470200 -2.40935600 -2.09103800 H 5.99988700 -3.59134700 -1.23299700 C 3.44475800 -2.17321600 1.16566800 H 3.07164300 -2.21099900 2.19480500 H 2.48189900 -1.18261200 0.73851200 C 0.14465800 -2.29598600 3.28930500 N -0.42017800 -1.62583400 2.52127700 C 0.84936400 -3.12657600 4.24030100 H 0.14688300 -3.58635400 4.94302900 H 1.39460000 -3.92263800 3.72160800 H 1.56748400 -2.52709000 4.80959800
7) – [CuII(tpa)(O2Cm)]+
7a
Energy: -1612.79766701 a.u.
41
C -1.66522600 3.00459100 -0.54824000 C -2.47745400 4.11950200 -0.38993900 C -3.70547400 3.96366000 0.24583100 C -4.08658200 2.69747000 0.68026400 C -3.22725700 1.62483300 0.46851000 N -2.02699800 1.78626900 -0.12039200 H -4.36215200 4.81705900 0.39943100 H -0.69280400 3.04846500 -1.03836400 H -2.14791700 5.08882500 -0.75387500 H -5.04492700 2.53795400 1.17105800 C -3.61097200 0.20489600 0.79496600 H -4.35882900 0.17110100 1.60489100 H -4.09166700 -0.23398100 -0.09216000 N -2.43862200 -0.62255300 1.09943300 C -1.92470100 -0.40951900 2.45722500 H -2.55477800 -0.89644200 3.22092600 H -1.97025900 0.67305400 2.65097900 C -0.49750800 -0.88068100 2.55701300 C 0.01918400 -1.44811300 3.71599500 N 0.25334600 -0.70462500 1.44985000 C 1.35564700 -1.83840200 3.74040000 H -0.62010800 -1.58047600 4.58694900 C 1.53497300 -1.10254900 1.47139000 C 2.12617700 -1.66544600 2.59631900 H 1.78233600 -2.28094900 4.63791500 H 2.08853900 -0.94520500 0.54662700 H 3.17094100 -1.96354600 2.56151700 C -2.64917300 -2.04101100 0.77526700 H -3.62028000 -2.40586800 1.14868800 H -1.87434000 -2.61334500 1.30560400 C -2.50514500 -2.28875300 -0.70594400 C -3.20111400 -3.29083500 -1.37308800 C -2.94613800 -3.49734600 -2.72657300 H -3.92729100 -3.90207900 -0.83991700 C -1.36810700 -1.70337200 -2.63824100 C -2.01102400 -2.69397200 -3.37158900 H -3.47636000 -4.27567900 -3.27104600 H -0.63247700 -1.02790300 -3.07488400 H -1.78622300 -2.82517600 -4.42669500 Cu -0.81537200 0.10921100 -0.19031000 N -1.61104100 -1.50713300 -1.33671500 O 0.36154400 0.83729400 -1.48929200 O 1.66511800 0.34099700 -1.24995000 C 2.58134200 1.43058300 -0.86763900 C 2.70731300 2.38092800 -2.05133200 H 3.05990200 1.85218700 -2.94274100 H 1.73200500 2.82581800 -2.27888900 H 3.41793900 3.18426200 -1.82712900 C 2.04913300 2.16303800 0.35255200 H 1.97877000 1.50914000 1.22922600 H 2.69506700 3.00986300 0.60934500 H 1.05095200 2.55669600 0.13741700 C 3.87108600 0.67110900 -0.61341300 C 4.60769600 0.81320700 0.56616600 C 4.33687200 -0.21941600 -1.58993000 C 5.78304800 0.09017900 0.76199700 H 4.27385200 1.50043600 1.34181000 C 5.50304100 -0.94948700 -1.39053000 H 3.76663200 -0.34680100 -2.50854300 C 6.23217000 -0.79537900 -0.21290100
42
H 6.35067600 0.22473100 1.68120800 H 5.84745900 -1.63830700 -2.15969300 H 7.15021700 -1.35927400 -0.05918800
7b
Energy: -1612.79060311 a.u.
C 0.90822900 -2.25278000 -0.05084500 C 0.98981300 -3.62397500 -0.26393200 C 0.08891900 -4.22131700 -1.13816800 C -0.85764100 -3.42348200 -1.77489300 C -0.86994500 -2.05711800 -1.52214200 N 0.00364100 -1.47852600 -0.67219800 H 0.11632300 -5.29361900 -1.31952900 H 1.57735800 -1.72811200 0.62929000 H 1.74462100 -4.20631700 0.25769200 H -1.58260500 -3.85346300 -2.46380500 C -1.81952300 -1.12416100 -2.22756700 H -1.28433800 -0.65650000 -3.06575600 H -2.66170800 -1.68455600 -2.66559000 N -2.28752900 -0.04396800 -1.34522600 C -2.53213800 1.23032600 -2.04027700 H -3.51305800 1.25080500 -2.54264800 H -1.77093900 1.32742400 -2.82688100 C -2.39046900 2.38893500 -1.08697200 C -3.13569500 3.55687800 -1.19691200 N -1.44660000 2.24169300 -0.13736600 C -2.88837500 4.60085700 -0.30927700 H -3.89650100 3.64602300 -1.97014200 C -1.20999400 3.24420100 0.72031600 C -1.90784500 4.44396400 0.66546300 H -3.45943400 5.52416100 -0.37630000 H -0.43103000 3.04334200 1.45637300 H -1.68761700 5.23404700 1.37813400 C -3.45804700 -0.44221200 -0.53343200 H -4.21351000 -0.94291200 -1.16139400 H -3.91468200 0.48547800 -0.15930500 C -3.07917000 -1.29373100 0.64895200 C -3.78237600 -2.43490500 1.01735300 C -3.38312900 -3.12563100 2.15983600 H -4.62804500 -2.77619800 0.42252500 C -1.64059500 -1.51248700 2.44223800 C -2.29517000 -2.65700200 2.88841000 H -3.91398300 -4.02234400 2.47235700 H -0.76653200 -1.10664400 2.95234500 H -1.95173100 -3.17012200 3.78291300 Cu -0.64791200 0.36586700 0.07303400 N -2.02736200 -0.84209500 1.35242000 O 0.62936000 0.87518400 1.38819000 O 1.91231200 0.36333600 1.09162900 C 2.77376300 1.39591800 0.49559800 C 2.10017600 1.98295100 -0.74005900 H 1.77843600 1.19165500 -1.43054300 H 1.22357300 2.57670100 -0.45844200 H 2.79803200 2.63374800 -1.27853300 C 3.01325600 2.47171100 1.53913500 H 3.47738100 2.05612600 2.43916800 H 3.65353300 3.27043400 1.14786200 H 2.05302600 2.91136200 1.82623900
43
C 4.00862400 0.59800500 0.11569800 C 5.27580000 0.88789200 0.62500100 C 3.87964000 -0.47044700 -0.78099500 C 6.38457200 0.13379500 0.24556400 H 5.40994300 1.71251700 1.32180600 C 4.98150800 -1.23060600 -1.15404500 H 2.89749000 -0.70671600 -1.19125800 C 6.24157700 -0.92858500 -0.64079600 H 7.36485100 0.37924300 0.64949800 H 4.85934100 -2.05771100 -1.85172300 H 7.10825100 -1.51788600 -0.93382800
7c
Energy: -1612.79286012 a.u.
C -2.08887200 -2.45578300 -0.93292000 C -3.26149400 -3.16270400 -1.16369600 C -4.39511400 -2.45959000 -1.56001000 C -4.31160000 -1.08025000 -1.72504300 C -3.09666000 -0.44473300 -1.49178000 N -2.00671500 -1.12710800 -1.09645900 H -5.33592600 -2.97713200 -1.73439800 H -1.17269100 -2.93219400 -0.58360200 H -3.28427700 -4.23990400 -1.02254800 H -5.17904300 -0.49916500 -2.03351800 C -2.90664300 1.03144700 -1.73892400 H -2.59349800 1.16361500 -2.78387900 H -3.86544700 1.56425800 -1.63824100 N -1.87374200 1.63072200 -0.87467400 C -0.97088000 2.55316100 -1.57680700 H -1.42960600 3.54230800 -1.74296600 H -0.77416400 2.12427700 -2.56941400 C 0.33713800 2.69250600 -0.84325400 C 1.07400400 3.86998600 -0.87782100 N 0.77994400 1.59164000 -0.19754300 C 2.31615300 3.91344500 -0.25010500 H 0.67816800 4.73940300 -1.39955800 C 1.97074800 1.64372100 0.42247300 C 2.77281100 2.77823300 0.40866800 H 2.91185100 4.82339600 -0.27268300 H 2.27370900 0.72782700 0.92575100 H 3.73507600 2.75783500 0.91394200 C -2.45280500 2.25307700 0.33343400 H -3.26629500 2.94764500 0.06510000 H -1.65571700 2.84945900 0.80038400 C -2.92118700 1.21081700 1.31121000 C -4.15847000 1.25445300 1.94311200 C -4.48252900 0.24281000 2.84530300 H -4.85522400 2.06451100 1.73397600 C -2.34915200 -0.74360400 2.40070900 C -3.56404000 -0.77491300 3.07969700 H -5.44408400 0.24860800 3.35417500 H -1.59073900 -1.51664300 2.52707600 H -3.78239800 -1.58261800 3.77347700 Cu -0.56281500 0.01661600 -0.12895500 N -2.03350800 0.22825100 1.54004200 O 0.30590500 -1.55164700 0.51332700 O 1.67116200 -1.31267400 0.74136400 C 2.51124900 -1.87331800 -0.33819400
44
C 2.49093900 -3.38960500 -0.20490100 H 2.85725000 -3.70385000 0.77762100 H 1.46608300 -3.75954300 -0.32642500 H 3.12270200 -3.85490100 -0.96995800 C 1.97945200 -1.44594100 -1.69478000 H 1.94678200 -0.35320700 -1.79251200 H 2.61175500 -1.84201600 -2.49683600 H 0.96889100 -1.84006700 -1.84123900 C 3.86594700 -1.28068700 0.00603900 C 4.63411300 -0.56964100 -0.91992100 C 4.34769500 -1.41070700 1.31574000 C 5.85459800 -0.00785400 -0.54996000 H 4.28792900 -0.45232700 -1.94510000 C 5.55819900 -0.83759200 1.68980400 H 3.75408100 -1.95209600 2.05077300 C 6.31789700 -0.13494500 0.75604800 H 6.44475000 0.53108500 -1.28911300 H 5.91356000 -0.94582500 2.71291300 H 7.27077600 0.30467300 1.04466700
8) – Self – Decomposition Structures (Tpa) (structure vii in Figure 8)
Energy: --1612.74308465 a.u.
C -2.13245200 -2.22350000 1.12975900 C -2.92626700 -3.29377800 0.73732500 C -3.09372100 -3.53120900 -0.62425100 C -2.45544500 -2.70420700 -1.54453400 C -1.66855300 -1.65872200 -1.07267900 N -1.52403300 -1.42880600 0.24287600 H -3.71584000 -4.35461900 -0.96834400 H -1.95229400 -1.97252000 2.17531200 H -3.40444700 -3.92229600 1.48369700 H -2.56167000 -2.86920300 -2.61522600 C -0.84725200 -0.77440100 -1.97707800 H 0.15362700 -1.22267100 -2.06408000 H -1.27242800 -0.74107800 -2.99325600 N -0.66849400 0.58131100 -1.42251100 C 0.62262400 1.19542900 -1.79105600 H 0.60863600 1.58653000 -2.82124000 H 1.38586800 0.40472300 -1.75090200 C 1.01392200 2.26364800 -0.80177500 C 1.92268100 3.27125000 -1.10824800 N 0.50603000 2.12651400 0.43347900 C 2.33008500 4.13476600 -0.09570400 H 2.31305300 3.36702100 -2.11993500 C 0.90742500 2.94339800 1.41255900 C 1.82137700 3.96568600 1.18914800 H 3.04265000 4.92905400 -0.30757700 H 0.48659000 2.73367900 2.39438100 H 2.12581200 4.61327600 2.00690300 C -1.79780800 1.48129000 -1.75217800 H -2.03957400 1.41347800 -2.82527900 H -1.45142300 2.50537800 -1.55824600 C -3.00835800 1.21518900 -0.89976700 C -4.27790700 1.02777800 -1.43557100 C -5.34713000 0.81729200 -0.56709900 H -4.42759400 1.04786100 -2.51402700 C -3.80244000 0.99007300 1.24900800 C -5.10770400 0.80035700 0.80218100
45
H -6.35150800 0.66695000 -0.95708500 H -3.56048100 0.97280100 2.31211700 H -5.91317700 0.64162600 1.51469000 Cu -0.56587000 0.35568500 0.69522100 N -2.77209600 1.19516400 0.42374200 O -0.06228400 0.00463300 2.41406200 O 1.53059100 -0.36515200 0.85253500 C 2.29886500 -1.42096600 1.35113200 C 2.87470200 -1.09034900 2.72232500 H 3.42967500 -0.14694400 2.70516700 H 2.04887500 -0.98175100 3.43391200 H 3.54670200 -1.88203600 3.07340200 C 1.50209300 -2.71681800 1.39863300 H 1.03235500 -2.93683000 0.43212100 H 2.12712100 -3.56908500 1.69070800 H 0.70764400 -2.59524200 2.14302400 C 3.34579300 -1.36938700 0.22651700 C 3.52438700 -2.41316500 -0.68964600 C 4.07769600 -0.18073000 0.05332500 C 4.45885500 -2.29453600 -1.71367700 H 2.96457500 -3.33933300 -0.57955600 C 4.99588200 -0.05871600 -0.98155000 H 3.90807300 0.65080000 0.73579600 C 5.19242700 -1.11807000 -1.86682000 H 4.61974700 -3.12843300 -2.39438200 H 5.56352500 0.86283300 -1.09727700 H 5.91716900 -1.02959900 -2.67379300
9) – Cyclohexadiene (CHD) Oxidation (Tpa)
9a (structure viii in Figure 8)
Energy: -1846.15236083 a.u.
C 1.72951600 -1.33066500 2.49124600 C 2.70090400 -2.15976300 3.03667700 C 4.03844800 -1.80664800 2.89194900 C 4.35006600 -0.63071200 2.21621000 C 3.32329500 0.15800300 1.70926300 N 2.02563900 -0.19184200 1.84010700 H 4.82835100 -2.43805800 3.29285300 H 0.66740000 -1.57313600 2.54019700 H 2.40826100 -3.06952000 3.55434400 H 5.38508300 -0.32018300 2.08132900 C 3.61061100 1.48745400 1.04833700 H 3.50061900 2.27227200 1.80983500 H 4.66394500 1.52148800 0.72013900 N 2.69064900 1.79819800 -0.04737400 C 2.24004300 3.18813800 -0.11862400 H 2.92789900 3.83093200 -0.69487400 H 2.23150000 3.58312200 0.90688700 C 0.83878500 3.29890200 -0.67369300 C 0.43500200 4.39287600 -1.43155900 N -0.02154700 2.31440800 -0.33712200 C -0.89338000 4.49163700 -1.83625500 H 1.15858000 5.16272100 -1.69467300 C -1.30294300 2.41330700 -0.73011000 C -1.78176100 3.48449800 -1.47157200 H -1.22670300 5.34111700 -2.42825800
46
H -1.94909900 1.58933300 -0.42239100 H -2.82977700 3.51728800 -1.75993200 C 3.14077700 1.28256700 -1.34550500 H 4.18387800 1.57827300 -1.55606600 H 2.51095500 1.75412100 -2.11443700 C 2.97836800 -0.21225600 -1.44763200 C 3.97703600 -1.04821900 -1.93505800 C 3.72757400 -2.41652300 -2.01649700 H 4.93566100 -0.63338900 -2.24268500 C 1.54159300 -1.99416800 -1.14120100 C 2.48681100 -2.89991900 -1.61396500 H 4.49459300 -3.09454200 -2.38485400 H 0.55046500 -2.31438800 -0.81027300 H 2.25252100 -3.96127800 -1.65519100 Cu 0.78787300 0.60205900 0.40647000 N 1.78020100 -0.68133400 -1.05586600 O -0.94208700 -0.49879300 0.40936600 O -1.36627600 -1.24292200 1.57838800 C -2.29363700 -0.42413700 2.35903500 C -1.59759600 0.85377500 2.79750800 H -0.67257200 0.60588100 3.33141400 H -1.33638400 1.49189200 1.94552200 H -2.23322600 1.43314200 3.47712700 C -0.73331100 -1.40482800 -3.59863100 C -1.64998400 -3.42896700 -2.46090900 C -2.38638000 -2.62417500 -1.66039500 C -1.47632600 -0.62921400 -2.77722300 H -0.12723500 -0.94781700 -4.38073700 H -1.74403300 -4.51129700 -2.37937700 H -3.06557500 -3.06595700 -0.93073900 H -1.46020300 0.45463700 -2.90758900 C -2.28612900 -1.17947900 -1.70691600 H -1.58709600 -0.86793200 -0.52472500 H -3.18452000 -0.61568200 -1.42826400 C -0.74197500 -2.89541800 -3.51970800 H -1.01651000 -3.32413200 -4.50223500 H 0.28939000 -3.27462100 -3.37379000 C -3.55119200 -0.20194400 1.53399200 C -4.25370700 -1.31560800 1.05724300 C -4.02450200 1.06995900 1.20204500 C -5.38656600 -1.16613200 0.26606200 H -3.89122500 -2.31541400 1.29556000 C -5.15859100 1.22555700 0.40444500 H -3.51170800 1.95743500 1.57070300 C -5.84170200 0.10917300 -0.06778000 H -5.91520100 -2.04676700 -0.09515800 H -5.51363900 2.22602700 0.16169400 H -6.72831500 0.22972200 -0.68700600 C -2.56107900 -1.31550700 3.56662500 H -3.28740900 -0.83433000 4.22973900 H -2.96534000 -2.28826400 3.27050300 H -1.63774000 -1.48410300 4.13311200
9b
Energy: -1846.14680416 a.u.
47
C -0.79657300 2.48219400 -0.15649800 C -0.88029500 3.81628500 0.22101600 C 0.17286100 4.66774700 -0.09450700 C 1.26446500 4.15089400 -0.78583100 C 1.27163900 2.80779600 -1.14569600 N 0.25184100 1.97956900 -0.83305100 H 0.15086200 5.71548100 0.19752400 H -1.57453000 1.76182400 0.09482000 H -1.75351000 4.16949900 0.76360700 H 2.11241700 4.78241200 -1.04676700 C 2.40122400 2.21960300 -1.95911400 H 2.09157100 2.20858300 -3.01356900 H 3.28646400 2.87678300 -1.90243100 N 2.71871400 0.84246200 -1.57682200 C 3.05516700 -0.05337600 -2.68290900 H 4.11976500 0.00062200 -2.96957800 H 2.47799200 0.27518800 -3.55855000 C 2.67242400 -1.47996900 -2.37106400 C 3.42917800 -2.55773200 -2.81705500 N 1.52485000 -1.65444100 -1.68089700 C 2.98972200 -3.85347700 -2.56207400 H 4.35387500 -2.37728500 -3.36266700 C 1.10645100 -2.90726700 -1.43694100 C 1.80167300 -4.03150000 -1.86033700 H 3.56841300 -4.70908800 -2.90270400 H 0.17455900 -2.98067700 -0.87482800 H 1.41798300 -5.02390000 -1.63857000 C 3.67731000 0.75293900 -0.46754500 H 4.57642000 1.36358400 -0.66332800 H 4.00438700 -0.29548700 -0.40962900 C 3.04591200 1.13606500 0.84552200 C 3.62248500 2.04932700 1.72095800 C 2.95765600 2.35583000 2.90642600 H 4.57195000 2.52081200 1.47199200 C 1.24348200 0.82020100 2.25224700 C 1.74416600 1.73263400 3.17697300 H 3.37889200 3.07754100 3.60316700 H 0.29133100 0.30706800 2.41166600 H 1.18435600 1.95237500 4.08353400 Cu 0.77157900 -0.01475500 -0.72521300 N 1.87543800 0.52719600 1.11110900 O -0.76338500 -0.98212100 0.22910600 O -2.08704000 -0.38046000 0.17470500 C -2.89496200 -1.04316100 -0.85531100 C -2.19541800 -0.93856800 -2.20558800 H -1.93251500 0.09888000 -2.44224200 H -1.27297500 -1.53162200 -2.21024700 H -2.84687400 -1.31362700 -3.00298900 C -3.09614800 -2.49919500 -0.47372600 H -3.52020300 -2.59669800 0.53184400 H -3.76071700 -3.00469700 -1.18313100 H -2.13286400 -3.02078500 -0.49134200 C -4.16663700 -0.20997100 -0.81244900 C -5.39326600 -0.74073000 -0.40487200 C -4.11717100 1.14123000 -1.17945400 C -6.53836100 0.05189200 -0.37495100 H -5.46983100 -1.78656500 -0.11607600 C -5.25611800 1.93680800 -1.14218800 H -3.17299000 1.57644100 -1.50508800 C -6.47396500 1.39256800 -0.74010100
48
H -7.48543600 -0.38433400 -0.06341000 H -5.19526600 2.98335900 -1.43569300 H -7.36929000 2.01059600 -0.71577100 C 1.22462500 -2.33127900 3.67364600 C -0.89048700 -1.21086500 4.38817600 C -1.51629100 -1.74212800 3.31193700 C 0.57129200 -2.84359900 2.60614700 H 2.27112900 -2.58154100 3.84450600 H -1.45273500 -0.60993100 5.10223600 H -2.57901900 -1.55243300 3.15960500 H 1.10403100 -3.50745400 1.92330100 C -0.81367600 -2.52824300 2.31815200 H -0.77876900 -1.66035000 1.19830100 H -1.39607800 -3.30269300 1.80611200 C 0.55043300 -1.46739000 4.68747900 H 0.65148500 -1.91817100 5.69324700 H 1.10066200 -0.51205100 4.79864800
9c
Energy: -1846.15636108 a.u.
C -1.26146300 -0.69252400 2.63393600 C -2.25303400 -1.22612600 3.44701100 C -2.66561000 -2.53565600 3.22211900 C -2.05760700 -3.26449900 2.20424300 C -1.06293500 -2.66572000 1.43833200 N -0.67653700 -1.39038800 1.64548900 H -3.45011100 -2.98420800 3.82775700 H -0.90877600 0.33357900 2.74740100 H -2.69602300 -0.62004000 4.23306000 H -2.35099800 -4.29322700 1.99979900 C -0.31143600 -3.43694700 0.37588900 H 0.61860700 -3.81309900 0.82541300 H -0.89120000 -4.32727500 0.07606200 N 0.05475100 -2.61211700 -0.77632000 C 1.38868900 -2.85578900 -1.32393400 H 1.41747200 -3.71655900 -2.01513600 H 2.04825800 -3.10367600 -0.47944100 C 1.94161000 -1.62557300 -2.00284900 C 2.81537800 -1.71466100 -3.08139300 N 1.58482900 -0.43741600 -1.47635200 C 3.34029900 -0.54857500 -3.63037700 H 3.07757800 -2.69130900 -3.48494100 C 2.08885900 0.68360500 -2.01198900 C 2.96768700 0.67645700 -3.08657800 H 4.02312500 -0.59702300 -4.47582400 H 1.76510800 1.60832800 -1.53356300 H 3.34843500 1.61292900 -3.48615900 C -0.98584500 -2.57294600 -1.81263700 H -1.28841400 -3.59071100 -2.11679700 H -0.54398200 -2.08746000 -2.69473500 C -2.18012400 -1.77313300 -1.36108300 C -3.48178000 -2.25705700 -1.43323300 C -4.52282700 -1.45936300 -0.96273300 H -3.67464900 -3.24802300 -1.84140700 C -2.89533100 0.20794500 -0.41940100 C -4.22475600 -0.20573200 -0.43999700 H -5.54946200 -1.81815500 -0.99512800 H -2.60651700 1.18170500 -0.01519100
49
H -5.00392900 0.44270500 -0.04501900 Cu 0.16152300 -0.46379900 -0.01368700 N -1.89297200 -0.55413100 -0.86823800 O 0.16345800 1.54808500 0.41331900 O 0.45464600 1.91930500 1.78929000 C 1.86861200 2.25111000 1.91423700 C -2.59708700 3.01062300 -2.39757900 C -3.32010000 3.82008900 -0.14767100 C -2.01984100 3.99569800 0.18726700 C -1.30822600 3.19435600 -2.02862700 H -2.83256400 2.66147500 -3.40234600 H -4.10514700 4.08904100 0.55842200 H -1.76675300 4.39712300 1.16937500 H -0.51403300 2.99115600 -2.74882000 C -0.93654000 3.63640400 -0.70172000 H -0.35684800 2.47332400 -0.05796700 H -0.01528500 4.22247000 -0.61786000 C -3.74274300 3.33111100 -1.49505100 H -4.40291000 4.07857900 -1.97589100 H -4.41022100 2.45193500 -1.40017300 C 1.98652500 2.52645500 3.40985800 H 3.02054700 2.78488400 3.66040500 H 1.33949800 3.36126100 3.70099500 H 1.70571300 1.64582000 3.99765300 C 2.70666200 1.04589300 1.51226800 C 3.80420100 1.13456300 0.65399800 C 2.36951600 -0.21094600 2.02915100 C 4.53590100 -0.00186200 0.30821400 H 4.09880100 2.09766900 0.23949100 C 3.09407300 -1.34782200 1.68584400 H 1.52261600 -0.29366300 2.70901600 C 4.18058000 -1.24737700 0.81666100 H 5.38786200 0.09074200 -0.36365300 H 2.81709700 -2.31243200 2.11274600 H 4.75805000 -2.13226800 0.55206400 C 2.16807100 3.50700100 1.11419000 H 1.46753600 4.29957500 1.39948100 H 3.18307000 3.86966300 1.31027000 H 2.07268900 3.33056900 0.03645700
9d
Energy: -1846.14697952 a.u.
50
C -1.47205000 1.86059000 1.59716600 C -2.37876700 2.81632300 2.03581100 C -3.67255600 2.41041300 2.34773400 C -3.99902400 1.06262100 2.22587900 C -3.03108500 0.16361400 1.79070000 N -1.78391700 0.56136600 1.46647200 H -4.41774200 3.13000300 2.67987200 H -0.45338700 2.12778600 1.31064900 H -2.07190300 3.85634100 2.12129900 H -4.99969200 0.70541100 2.46499900 C -3.30285300 -1.32236200 1.72253200 H -2.93594500 -1.77508000 2.65430900 H -4.39044300 -1.50684300 1.69889600 N -2.61723000 -1.97674700 0.60564000 C -1.99445200 -3.26128100 0.91754900 H -2.70995800 -4.10212200 0.89506500 H -1.61674300 -3.19720900 1.94821100 C -0.82866800 -3.54852100 0.00309200 C -0.51984800 -4.84548900 -0.39029800 N -0.06566000 -2.49237500 -0.35630400 C 0.61913300 -5.07359700 -1.15670700 H -1.16735600 -5.66742600 -0.08950000 C 1.03573800 -2.71811400 -1.09535500 C 1.41446700 -3.98894600 -1.50864200 H 0.87832800 -6.08164000 -1.47286300 H 1.62530700 -1.83414700 -1.33169800 H 2.31755600 -4.11567800 -2.09965200 C -3.42794700 -2.02510900 -0.61519800 H -4.41181300 -2.49229700 -0.43083200 H -2.89406100 -2.66464000 -1.33354000 C -3.59308300 -0.65215500 -1.20811200 C -4.83137900 -0.13947600 -1.57907600 C -4.89906400 1.14644200 -2.10948300 H -5.72999900 -0.74042600 -1.44881500 C -2.52693000 1.28199700 -1.86206100 C -3.72324900 1.87469600 -2.25230300 H -5.85625500 1.57308700 -2.40139800 H -1.57767400 1.81048800 -1.95302200 H -3.72680300 2.88288300 -2.65900800 Cu -0.84264400 -0.64240200 0.03132300 N -2.45199000 0.04928600 -1.34899000 O 0.64046600 0.73608600 -0.35899100 O 1.97177700 0.16381500 -0.40158500 C 2.61026900 0.23494300 0.91981900 C 2.78121500 1.68729300 1.34151600 H 3.43379600 2.22808700 0.65047200 H 1.80870800 2.19786800 1.36402900 H 3.21938700 1.74125800 2.34458900 C 1.77216200 -0.51419400 1.94212000 H 1.58349800 -1.54854700 1.63178000 H 2.27471500 -0.53096700 2.91604400 H 0.80663000 -0.01263100 2.07667500 C 3.94465800 -0.42339100 0.60996500 C 4.38764000 -1.57072100 1.27227400 C 4.75489100 0.12778300 -0.39172500 C 5.61820600 -2.14260700 0.95591300 H 3.78031500 -2.02247600 2.05410600 C 5.97735000 -0.44846400 -0.71589000 H 4.41173200 1.01331200 -0.92664000 C 6.41518200 -1.58535200 -0.03893900
51
H 5.95369400 -3.02845400 1.49211700 H 6.59314600 -0.00734100 -1.49754900 H 7.37592300 -2.03305400 -0.28571700 C 3.02579100 4.09060000 -1.14100700 C 2.27872700 3.21070500 -1.84750500 C 0.24153200 3.97709000 -0.69612400 C 0.96198300 4.84721700 0.04626000 H 4.08891600 4.19961300 -1.35415100 H 2.74472000 2.61142400 -2.62961600 H -0.84726800 3.96541200 -0.60510900 H 0.46016600 5.53367800 0.72798400 C 0.86655300 3.02333800 -1.59271400 H 0.27174600 2.69313300 -2.45271700 H 0.76874900 1.77178400 -0.90526100 C 2.44831100 4.95150800 -0.06566600 H 2.92129000 4.70943800 0.90746200 H 2.74189500 6.00534600 -0.22210800
9e
Energy: -1846.15326491 a.u.
C 1.64164500 1.30850500 1.58710900 C 2.34429500 2.33392200 2.20558200 C 1.64334400 3.46312500 2.61725500 C 0.26796200 3.51097100 2.40787900 C -0.36533900 2.43942400 1.78650200 N 0.31834500 1.35484100 1.36969700 H 2.15748500 4.29547000 3.09297700 H 2.14726300 0.41201900 1.22341600 H 3.41861300 2.24452000 2.34933400 H -0.31587600 4.37546600 2.72083900 C -1.86671100 2.39940000 1.60835800 H -2.29085400 1.83050300 2.44794100 H -2.28257700 3.41922600 1.68478800 N -2.27451000 1.73518400 0.37056600 C -3.44339400 0.86514900 0.48049400 H -4.39660300 1.42018100 0.42560000 H -3.40579400 0.38920600 1.47102400 C -3.41840300 -0.22578800 -0.56213200 C -4.59425000 -0.75615200 -1.08245100 N -2.20647100 -0.69382300 -0.92482600 C -4.52446100 -1.80275800 -1.99624100 H -5.55375100 -0.34693200 -0.77049800 C -2.14261500 -1.70239200 -1.80975800 C -3.27366600 -2.28398700 -2.36745500 H -5.43284300 -2.22909700 -2.41647100 H -1.13731300 -2.04751100 -2.04738900 H -3.16863400 -3.09625800 -3.08211200 C -2.36358900 2.65372200 -0.77026900 H -3.01355500 3.51731000 -0.54181200 H -2.83570700 2.10036900 -1.59473800 C -0.99978400 3.11463200 -1.20879200 C -0.68243500 4.45808200 -1.37988100 C 0.60907200 4.80244900 -1.77171700 H -1.43701200 5.22285000 -1.20190700 C 1.12898300 2.47128300 -1.79961600 C 1.53684300 3.78882500 -1.98349700 H 0.88555500 5.84621600 -1.90458200 H 1.81749500 1.64018600 -1.95532200
52
H 2.55708500 4.00850600 -2.28891900 Cu -0.58416800 0.28001400 -0.17541700 N -0.10557300 2.13040200 -1.41729200 O 1.07472100 -0.88929300 -0.60188100 O 0.87026700 -2.28078900 -0.94864700 C 0.85408500 -3.12566300 0.25347000 C 2.12156500 -2.92259700 1.06760400 H 2.99385800 -3.23455600 0.48507600 H 2.26752000 -1.87284200 1.34275700 H 2.08125500 -3.51427300 1.98905800 C 4.96867300 -2.32760700 -0.96000700 C 4.01381400 -1.80840700 -1.76697900 C 4.16452100 0.35158500 -0.59912800 C 5.10011000 -0.14323000 0.24290200 H 5.34652400 -3.33384400 -1.13828200 H 3.62050500 -2.40330100 -2.59089800 H 3.89520000 1.40919300 -0.53943500 H 5.58491100 0.50888000 0.96933500 C 3.47542900 -0.48097800 -1.56435100 H 3.09022100 0.01697300 -2.46177300 H 2.15565900 -0.70280900 -1.00010100 C 5.55362100 -1.56574200 0.18392300 H 5.32261700 -2.08041200 1.13890300 H 6.65727400 -1.60898700 0.14747800 C 0.86099500 -4.50898200 -0.38299400 H 0.73507800 -5.28302200 0.38159500 H 0.06081100 -4.62124400 -1.12229900 H 1.81346000 -4.67587400 -0.89604500 C -0.41357200 -2.82787500 1.04478100 C -0.42980400 -1.80602400 2.00170200 C -1.60944500 -3.51449800 0.80299700 C -1.59693500 -1.47798800 2.68948000 H 0.48539500 -1.26274500 2.22725300 C -2.77876100 -3.19188400 1.48634300 H -1.63696000 -4.32201700 0.07381100 C -2.77801900 -2.17059800 2.43397600 H -1.57143000 -0.69170200 3.44475400 H -3.69152200 -3.75101400 1.28615500 H -3.68756300 -1.93216600 2.98427200
9f
Energy: -1846.14536742 a.u.
C -0.43539900 -1.99008000 1.18532700 C -0.53320900 -3.31404400 1.59286500 C 0.55955900 -3.90015600 2.22234800 C 1.70439600 -3.13325600 2.42144100 C 1.72513100 -1.81252900 1.98758500 N 0.66613500 -1.24415700 1.37186200 H 0.52640100 -4.93736600 2.54876600 H -1.26324900 -1.49550600 0.67758800 H -1.45160200 -3.86646400 1.40817400 H 2.58247300 -3.55370600 2.90925800 C 2.91385400 -0.91479800 2.23021100 H 2.68298200 -0.26720900 3.08773200 H 3.79202000 -1.51812300 2.51980300 N 3.19566700 -0.04774600 1.08711400 C 3.66395100 1.29625500 1.42283200 H 4.74735000 1.33654000 1.63112000
53
H 3.15328700 1.59684300 2.34890800 C 3.30548500 2.28024300 0.33684200 C 4.16051100 3.31389100 -0.02772700 N 2.08826900 2.12837600 -0.22904600 C 3.75147900 4.22991600 -0.99266200 H 5.13689100 3.39756100 0.44665900 C 1.69795600 3.01392400 -1.16200100 C 2.49468000 4.07718800 -1.56799200 H 4.40617900 5.04545500 -1.29175400 H 0.70110200 2.84669100 -1.56866600 H 2.13184000 4.76623500 -2.32620800 C 4.01208600 -0.69497700 0.05561300 H 4.87614600 -1.22229900 0.49720800 H 4.42008100 0.10302700 -0.58211700 C 3.21403600 -1.62883500 -0.81922700 C 3.68582100 -2.88403600 -1.18980500 C 2.92043600 -3.66831700 -2.04921400 H 4.64198200 -3.24025700 -0.80959400 C 1.31236200 -1.90389800 -2.09248300 C 1.70961200 -3.16786300 -2.51548300 H 3.26633700 -4.65519500 -2.34913000 H 0.37134300 -1.46307400 -2.42411900 H 1.08115200 -3.74147500 -3.19254600 Cu 1.14014600 0.35038100 0.10940200 N 2.03709500 -1.14781000 -1.26069900 O -0.79676600 0.55364200 -0.57499300 O -1.25426900 1.89030400 -0.88357500 C -1.89031200 2.52300700 0.28191600 C -4.74335000 -0.78623200 -1.58183100 C -3.63205200 -0.21358800 -2.09801400 C -2.34597500 -2.26682500 -1.66343500 C -3.43559500 -2.86028000 -1.12602300 H -5.68505400 -0.23980500 -1.57857800 H -3.68488400 0.79474200 -2.50889000 H -1.42099500 -2.84119600 -1.75652000 H -3.38702800 -3.90033900 -0.80256200 C -2.34858400 -0.88319600 -2.10030400 H -1.68571800 -0.63625300 -2.94012700 H -1.54448600 -0.13200000 -1.20077800 C -4.75086400 -2.16602700 -1.01638000 H -5.08232700 -2.13328800 0.03976400 H -5.53754100 -2.77406400 -1.50126000 C -2.22593000 3.88643500 -0.30577000 H -2.75337100 4.50085800 0.43134100 H -1.30589300 4.40938700 -0.58828400 H -2.85244900 3.79723800 -1.19920400 C -0.87198200 2.67908000 1.40472700 H -1.33950800 3.14259200 2.28113100 H -0.45883400 1.71210800 1.71793100 H -0.03883400 3.31334000 1.08085900 C -3.10941900 1.73769400 0.73863700 C -4.41243800 2.15076900 0.44395700 C -2.94685100 0.57250600 1.49962000 C -5.51428500 1.42837400 0.89517900 H -4.58295200 3.05730800 -0.13293300 C -4.04329300 -0.16445500 1.93332500 H -1.94569800 0.24926100 1.77479700 C -5.33530000 0.26413900 1.63613300 H -6.51861400 1.78193100 0.66794600 H -3.88658100 -1.06819600 2.52281400
54
H -6.19716200 -0.29873200 1.99149200
II – Calculated UV-Vis Spectra
TD-DFT spectra (see Computational Methods section for details) generated by applying Gaussian broadening to
computed peak positions and scaling arbitrary absorption intensities to predicted oscillator strengths.
a) [CuII(bpa)(CH3CN)(O2Cm)]+
b) [CuII(bpa)(O2Cm)]+
55
c) [CuII(tpa)(O2Cm)]+
III - Selected M06-L vibrational frequencies (cm–1) with mode assignment and 18O2 isotope shift
56
a) Computed for structure i
896.5 (Δν =32.7) — mixed O–O stretching mode
812.4 (Δν = 15.4) — mixed O–O stretching mode
619.4 (Δν = 7.4) — C–C–O deformation mode
499 (Δν = 16) — Cu–O stretching mode
b) Computed for structure ii
903.4 (Δν =41.6) — mixed O–O stretching mode
833.4 (Δν = 17.2) — mixed O–O stretching mode
604.8 (Δν = 7.9) — C–C–O deformation mode
515.7 (Δν = 15.7) — Cu–O stretching mode