supporting information - stahl...
TRANSCRIPT
S1
SUPPORTING INFORMATION
Reaction of O2 with [(–)-Sparteine]Pd(H)Cl: Evidence for an Intramolecular [H–L]+ "Reductive Elimination" Pathway
Nattawan Decharin, Brian V. Popp and Shannon S. Stahl*
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706
Table of Contents Page General experimental considerations S2 General procedure for the synthesis of (Sp)Pd(H)Cl S2 General procedure for in situ kinetic study of oxygenation S2 NMR spectra of the reaction of (Sp)PdCl2 with (EtO)3SiH and the in situ oxygenation reaction S3 Representative reaction time courses for the in situ oxygenation of (Sp)Pd(H)Cl S3 Computational methods S4-5 Computational Study of the Oxygenation and Protonolysis of Zwitterionic Complex 3 To Form (Sp)Pd(OOH)Cl. S6-9 Computational Studies of H–Ligand Reductive Elimination from (N-N)Pd(H)Cl Complexes. S10-12 Full Gaussian 03 and Gaussian 09 reference S13 Total energies, thermochemical analysis, and three lowest frequencies from normal mode analysis S14-16 Cartesian coordinates for optimized complexes S17-33 References S34
S2
General Experimental Considerations
All procedures, except for the oxygenation reaction, were carried out under N2 atmosphere. (Sp)PdCl2 was prepared according to the literature procedure.1 (EtO)3SiH, 1,3,5-trimethoxybenzene (NMR internal standard), and oxygen gas were used without purification. CD2Cl2 was dried over CaH2, distilled, and deoxygenated prior to used. NMR data were recorded using Varian INOVA-500 spectrometer. 1H chemical shifts were referenced to residual protons in the deuterated solvent at 5.32 ppm.
General Procedure for the Synthesis of (Sp)Pd(H)Cl Complex A stock solution of internal standard (5.0 mM 1,3,5-trimethoxybenzene) in CD2Cl2 was
prepared in an N2 atmosphere glovebox. Stock solution of (Sp)PdCl2 (9.0 mM) and (EtO)3SiH (184.2 mM) were prepared by dissolving them in the internal standard solution. The solutions of (Sp)PdCl2 (200 µL) and internal standard (300 µL) were added to a J-Young NMR tube of known volume then the NMR tube was placed in a cold well inside the glovebox (with liquid N2 cooling the well). Once the solution in the NMR tube was frozen, 100 µL of (EtO)3SiH solution was added to the tube and allowed to freeze. The NMR tube was then quickly taken out of the glovebox and placed in an acetone/dry ice cooling bath. The NMR tube was inserted into the pre-cooled (–10 °C) NMR spectrometer, and the reaction was monitored. Once (Sp)PdCl2 was mostly consumed and the hydride resonance at –25.9 ppm appeared, the NMR tube was taken out of the spectrometer and quickly placed in an acetone/dry ice bath. The concentration of the Pd-hydride species was established by 1H NMR spectroscopy at –30 °C.
General Procedure for in situ Kinetics Study of Oxygenation
The J-Young NMR tube containing Pd-hydride species prepared by the procedure
described above was kept in an acetone/dry ice bath while it was connected to a gas manifold equipped with a volume-calibrated mercury manometer. The headspace of the NMR tube was evacuated, and the NMR tube was fill with the desired amount of oxygen gas. Elevated pressures of O2 were achieved by cooling the tube with liquid N2. The tube was then sealed and kept in an acetone/ dry ice bath. The NMR tube was taken out of the cooling bath and shaken right before it was inserted into the pre-cooled (–30 °C) NMR spectrometer. Multiple scans were taken for each data point. The reaction was monitored until the hydride resonance at –25.9 ppm completely disappeared. The observed rate constants were determined by a nonlinear least-squares fit of an exponential function to the reaction timecourses, where the values for [Pd-hydride]0, kobs, and [Pd-hydride]∞ were floated, using the Solver function within Microsoft Excel.
S3
NMR spectra of the reaction of (Sp)PdCl2 with (EtO)3SiH and the in situ oxygenation reaction
Figure S1. NMR spectra of (Sp)PdCl2, in situ generated (Sp)Pd(H)Cl and the reaction mixture of the in situ oxygenation of (Sp)Pd(H)Cl.
Representative Reaction Timecourses for the in situ Oxygenation of (Sp)Pd(H)Cl
0
0.2
0.4
0.6
0.8
1
0 1000 2000 3000 4000 5000
(Sp)Pd(H)Clfit
Conc
entra
tion
(mM
)
Time (s)
O2 = 1 atm
0
0.10.20.30.40.50.60.7
0 1000 2000 3000 4000 5000
(Sp)Pd(H)Clfit
Time (s)
Conc
entra
tion
(mM
)
O2 = 2.8 atm
0
0.10.20.30.40.50.60.7
0 1000 2000 3000 4000 5000
(Sp)Pd(H)Clfit
Conc
entra
tion
(mM
)
Time (s)
O2 = 4.3 atm
Figure S2. Representative time courses for the in situ oxygenation of (Sp)Pd(H)Cl. Reaction conditions: [Pd-H] = 0.53 – 0.92 mM, pO2 = 1.0 – 4.3 atm, CD2Cl2, –30 °C, 600 µL.
S4
Computational Methods All computations were performed with the Gaussian 03 (G03) program2 unless specified
otherwise. Spin-restricted density functional theory (RDFT) was used for all species in which the dioxygen moiety was not involved. A spin-unrestricted (UDFT) methodology was used for molecular oxygen and Pd-O2 species. Geometry optimizations were performed using the B3LYP functional.3 A basis set combination of the Stuttgart RSC 1997 ECP (quasi-relativistic ECP28MWB) for Pd4 and the 6-31+G(d) for all other atoms were used. Spherical polarization functions (5D) were used throughout. Frequency calculations were performed at the optimized geometries using the same basis sets to confirm that each optimized ground state has no imaginary frequencies and each optimized transition state has a single imaginary frequency. Zero-point energy, thermal corrections, and entropic corrections were calculated from the normal-mode analysis. Single-point solvation energies (toluene solvent at 298.15 K) were calculated at the stationary points with the Pd basis detailed above and the 6-311+G(d,p) basis for all other atoms using the integral-equation-formalism polarizable-continuum model (IEF-PCM).5 The Gibbs free energy reported here was corrected for the change in concentration from gas phase to the 1 M standard-state solution conditions by including a correction for translational entropy.6 In general, we expect that standard KS-DFT calculations will yield relative energy differences that are accurate on average to ~3-5 kcal/mol.7 Spin density, charge analyses, and natural bond orbital analyses were calculated using the natural population analysis method8 as implemented within NBO 5.9 in G09.2
Excited electronic states of O2 or Pd-O2 species were calculated as single-point energies using spin-unrestricted DFT methods at the triplet-optimized structures. The electronic configuration of the converged SCF wavefunctions was confirmed by the <S2> values, which is ~1.0 for a spin-contaminated open-shell singlet (OSS), 0 for a close-shell singlet (CSS), and ~2.0 for an open-shell triplet (OST) states. The spin-contaminated OSS total energy is corrected by using a spin-projection method reported by Yamaguchi, Jensen, Dorigo, and Houk (eq S1).9 This treatment yields a singlet-triplet energy difference of 20.5 kcal/mol for molecular oxygen (expt. 22.3 kcal/mol).
!
1Espin"corrected "DFT =1EUDFT +
1S2
3S2 "
1S2
1EUDFT "3EUDFT[ ] (S1)
An estimate for the geometry and energy at which the triplet and singlet potential energy
surfaces cross, the minimum energy crossing point (MECP), was carried out by the following method. The high-energy triplet species, predicted after the crossing point is subjected to geometry optimization, leading to relaxation to a lower energy, more stable, triplet species. At each geometry along this optimization pathway, both solvation-corrected unrestricted triplet and singlet single-point energy calculations were performed with the Pd basis detailed above and the 6-311+G(d,p) basis for all other atoms. The geometry where the two surfaces intersect was used as the starting point for the MECP calculation using an algorithm developed by Harvey et al.10 The algorithm utilizes energy gradient and total energy inputs from separate OST and OSS state calculations at a single geometry to construct two new hybrid gradients that are orthogonal and define the crossing hyperline. A steepest-descent approach11 is then utilized to perform a geometry optimization with the hybrid gradients. This calculation was performed in the gas-
S5
phase, and the optimization calculation yielded a MECP in which the difference in total energy between the singlet- and triplet-spin surfaces is less than 1.1 kcal/mol. The OSS energies were not corrected for triplet spin-contamination; however, as one can derive from equation S1, the correction becomes negligible when the surfaces converge in energy. A rigorous multi-configurational analysis is needed to obtain a quantitative assessment of the MECP, but this is outside of the scope of the present study. Because similar issues do not plague the OST state, we suggest that the optimized MECP, using standard KS-DFT theory, provides a qualitatively accurate geometry and lower-energy limit. A single-point solvation energy calculation (as detailed above) was performed at the geometry-optimized MECP. Rigorous thermochemical calculations were not performed on the optimized MECP. Instead, an estimate of the Gibbs free energy of the MECP was obtained by adding the averaged thermal and entropic corrections calculated from the ground-state-optimized intermediates (4 and 5) that flank the intersection of singlet and triplet surfaces. These values were used to position the MECP on the free energy diagrams reported in this work.
S6
Computational Study of the Oxygenation and Protonolysis of Zwitterionic Complex 3 To Form (Sp)Pd(OOH)Cl. Aerobic oxidation of zwitterion 3 yields Pd-hydroperoxide (9) via an oxygenation/protonolysis sequence (Figure S3) similar to that reported for other Pd0 systems.12 The HLRE pathway proceeds via 2TS. An IRC analysis probing the forward potential energy surface (ie., toward intermediate 3) reveals a surface that is downhill with no evidence of additional intermediates or transition states (Figure S4A). Evaluation of the RMS gradient along this surface illustrates a significant event labeled as A (Figure S4B). Although the surface is not defined well-enough to characterize these geometries as true stationary points or saddle points, visualization of the geometries suggest similarities to intermediates and transition states characterized for other nitrogenous donor ligand systems (see below, Figures S6-S8). IRC analysis in the reverse direction proved to be a challenge, so we characterized the reverse direction by performing a geometry optimization of a species slightly to the reactants side of 2TS
and we performed a relaxed-potential-energy surface scan following the motion of the N1-N2-Pd-H dihedral twist that defines the motion of the saddle point imaginary frequency. The former optimization calculation relaxed directly to 1 providing substantial evidence that 2TS is connected directly to 1. The latter RPES calculation provided a full detailed picture of the energy surface from 1 to 3, revealing that 2TS is the only barrier on the energy landscape between species 1 and 3.
Oxygenation of zwitterion 3 provides linear end-on triplet superoxide 4 in which SpH+ has dissociated (Pd-NA bond length > 3.5 Å); however, the hydrogen bonding interaction is maintained, as evidenced by an NBO analysis. The interaction stabilizes the zwitterion significantly in non-polar solvent (ΔΔG° = +16.6 kcal/mol for separated species). Coordination of O2 oxidizes the Pd center, resulting in an increase in the natural charge on Pd from –0.015 to +0.382. The O–O bond length increases from 1.22 Å (free molecular oxygen) to 1.30 Å. A RPES scan was performed to characterize the O2 bindng event in which the Pd–O2 separation was stepped in 0.1 Å increments from 3.0 –2.2 Å (Figure S5). No structural rearrangement of the initial geometry observed in 3 occurs until a Pd–Oα separation of 2.2 Å is achieved. At this geometry, ligand rearrangement, leading directly to a species similar to 4, occurs with minimal perturbation in the total energy surface. A number of saddle point guesses were extracted from the RPES calculation around this region, and these geometries were subjected to full transition-state optimization. No calculations proved fruitful as the potential energy surface is likely more-or-less flat and/or poorly defined in this region. After traversing the minimum-energy crossing point (MECP), an η2-peroxide species 5 is formed in which the hydrogen bonding interaction occupies a square-planar coordination site. Chloride ligand isomerization via 6TS brings the Lewis-basic NA back into the PdII square plane thus enabling ligand reassociation in complex 7. This process also positions the ammonium arm of Sp (ie., NB-H+) over the axial face of the square plane thus facilitating Pd-peroxide protonolysis via 8TS.
S7
0.0
18.6
10.7
PdH Cl
PdCl
H
–12.0
+ O2
+ O2
+ O2
Triplet State (S=1)
NA NB
NA NB
10.4
13.8
OPd ClO
NA
NBH
20
10
0
–20
OPd ClO
NA
NB
HO
Pd
Cl
O
NA NBH
15.0
8.8
O
Pd
Cl
O
NA NBH
O
Pd
Cl
O
NA NBH
12.8
21.422.8
Singlet State (S=0)
MECP
1
2TS
34
57
6TS 8TS
9
O
Pd
Cl
O
NA NBH
{0.0}
{21.7}
{11.8}{11.1}
{1.4} {0.3}
{0.9}
{–5.3}
{–0.4}
{–27.9}
PdCl
HNA NB
–10
NA NBNA NB =
MECP
PdCl OOH
NA NB
30Fr
ee E
nerg
y {T
otal
Ene
rgy}
(kca
l/mol
)
Figure S3. Reaction profile for the reaction of (Sp)Pd(H)Cl complex with O2 to form (Sp)Pd(OOH)Cl. The position of the MECP on the free energy diagram was estimated using the averaged thermal and entropic corrections of flanking ground-state intermediates 4 and 5. See the Computational Methods discussion above for more details.
S8
Figure S4. Energy profiles describing the HLRE pathway via 2TS. (A) IRC energy profile from 2TS in the “forward” direction. (C) Relaxed potential energy surface scan over the entire HLRE pathway (calculation specifics: scan N1-N2-Pd-H dihedral angle from 5° to 177° by 2° increments).
S9
Figure S5. Energy profile for the reaction of zwitterionic complex 3 with O2 to form superoxide adduct 4.
S10
Computational Studies of H–Ligand Reductive Elimination from (N-N)Pd(H)Cl Complexes.
With different N-chelating ligands, one would expect differences in the bond strength of
Pd–N bond as well as the basicity of the nitrogen to impact the energetics of the deprotonation step. To show the generality of our proposed mechanism to other catalyst systems containing N-chelating ligands we extended our study to other (N-N)Pd(H)Cl complexes (N-N = phen, bpy, and py-ox). Ground state structures for these complexes were computed. In the case of py-ox ligand, both isomers were identified. The lower energy isomer has the hydride ligand trans to pyridine (ΔG = 1.8 kcal/mol), consistent with oxazoline being a slightly better donor than pyridine (pKa’s for pyridinium and oxazolinium are 5.2 and ~5.5 respectively).13 The Pd–N bond lengths in these complexes shows the expected trends (Table S1). The Pd–N(trans to hydride) bonds are longer than the Pd–N(cis to hydride) bonds with the Pd–N bonds in the (–)-sparteine complex being longer than the others. These observations are consistent with the weak π-accepting ability of pyridine-based ligands, which results in stronger Pd–N bonds.
Table S1. Selected Bond Lengths and Bond Angles for the Calculated (N-N)Pd(H)Cl Complexes
N-N ligand N–Pd–N (degree) Pd–Ntrans (Å) Pd–Ncis (Å) Pd–H (Å) Pd–X (Å) sp 84.77 2.33 2.18 1.53 2.33
phen 78.72 2.20
2.08 1.54 2.31 bpy 77.85 2.18 2.07 1.54 2.31
py-ox (lower E isomer) 76.70 2.24 2.07 1.54 2.31 py-ox (higher E isomer) 77.54 2.21 2.09 1.54 2.30 * trans and cis are relative to hydride ligand
The reaction profiles for the ligand-assisted reductive elimination for py-ox and phen systems are shown in Figure S4 and S5 respectively. The transition states for κ2-to-κ1 isomerization were similar to those in the Sp ligand system, which featured the dissociation of one of the arms of the ligand along with rotation about Pd–N bond. In the case of pyridine-oxazoline ligand, the barrier of this step was shown to be lower in energy for the more stable isomer (hydride trans to pyridine). In contrast to the sp system, stable intermediates of (κ1-N-N)Pd(H)Cl were located. This feature presumably arises because pyridine-based ligands are weaker general bases relative to Sp. Deprotonation transition states from these intermediates to produce zwitterionic Pd0 species appeared to be slightly lower in energy than κ2-κ1 isomerization.
S11
(A)
N N
O
PdCl H
0.0
14.8
N N
O
PdH
Cl
!G
{!E}
(kca
l/mol
)
-10
0
10
20
N N
O
PdH
Cl
14.0
N N
O
PdH
Cl
14.7
N N
O
PdH
Cl
16.3
30
40
A
BTS
C
DTS
E
{0.0}
{17.5} {16.6} {17.3}{16.2}
(B)
N N
O
PdH Cl
1.8
17.9
N N
O
Pd
Cl
H
16.7
N N
O
Pd
Cl
H
17.7
N N
O
Pd
Cl
18.9
N N
O
Pd H
Cl
-10
0
10
20
H
30
40
F
GTS
H
ITS
J
!G
{!E}
(kca
l/mol
)
{2.1}
{21.6} {21.0} {20.0} {18.3}
Figure S6. Reaction pathways for reductive elimination from (py-ox)Pd(H)Cl complexes
S12
N NPd
Cl H
0.0
21.4
-10
0
10
2019.2 19.1 18.2
N N
PdCl
H
N N
PdCl
H
N N
PdClH
N N
PdCl
H
K
LTS
M
NTS
O
30
40
!G
{!E}
(kca
l/mol
)
{0.0}
{24.7} {23.3} {21.9} {20.0}
Figure S7. Reaction pathways for reductive elimination from (phen)Pd(H)Cl complex
Due to the flexibility of the bpy ligand, one pyridine ring dissociates by rotating out of the square plane. A separate transition state was located for the rotation about Pd–N bond, which brings the hydride ligand and the unassociated pyridine into close proximity, allowing for deprotonation of the hydride by the disassociated nitrogen atom (Figure S6). The first step was determined to be the highest energy barrier of this pathway.
N NPd
Cl H
0.0
-10
0
10
2019.2 19.1
N
N
PdCl
HN N
PdClH
N N
PdCl
H
20.2
N N
PdCl H
19.7 17.7
N
N
PdCl
H
N
NPd
Cl H
15.5
P
QTS
R
STS
T
UTS
V
30
40
!G
{!E}
(kca
l/mol
)
{0.0}
{22.6}{17.5}
{22.5} {20.8} {22.0} {20.6}
Figure S8. Reaction pathways for reductive elimination from (bpy)Pd(H)Cl complex
S13
Full Gaussian 03 and Gaussian 09 Reference
Gaussian 03, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
S14
Solvation-Corrected Energies and Thermochemical Corrections at 298K (kcal/mol) and Three Lowest Frequencies from Normal-Mode Analysis
NA-NB = Sp = (–)-sparteine
Label Description Total E ZPE H S Frequencies (cm-1) Esol s2 Gsol 3O2 3Sg
– state -94358.87 2.33 -94354.45 48.98 1633.4 -94356.90 2.009 -94368.98 1 Pd(NA-NB)(H)(Cl) - H cis to NA -806694.92 259.46 -806424.00 130.62 51.0, 92.8, 99.2 -806817.23 0.000 -806587.15 1_HAATS TS HAA by O2 -901010.97 259.85 -900737.55 151.66 -1578.1, 25.1, 47.9 -901160.32 2.024 -900934.01 2TS TS κ2-κ1 isomerization -806674.00 257.29 -806405.00 134.66 -145.0, 47.7, 54.9 -806795.54 0.000 -806568.57 3 Pd(κ1-NA-NBH)Cl -806680.37 259.22 -806409.49 134.39 41.4, 64.3, 80.2 -806805.38 0.000 -806576.47 4 Pd(η1-O2)Cl---SpH+ (OST) -901029.48 264.89 -900750.54 158.83 26.5, 41.0, 50.7 -901177.08 2.010 -900947.38 Pd(η1-O2)Cl---SpH+ (OSS) -901169.67 0.949 -900939.98 Pd(η1-O2)Cl---SpH+ (SC-singlet) -901163.05 Spin-corr -900933.36 MECP MECP (OSS) -901173.10 0.376 -900942.70 MECP (OST) -901172.05 2.012 -900941.65 MECP (SC-Singlet) -901173.34 Spin-corr -900942.94 5 Pd(η1-O2)Cl---SpH+ (CCS) -901027.26 265.31 -900748.16 154.63 19.4, 36.6, 49.4 -901174.45 0.000 -900943.34 Pd(η1-O2)Cl---SpH+ (OST) -901165.86 2.012 -900934.75 6TS TS for SpH+ reassociation to Pd(η2-O2)Cl- -901024.86 264.89 -900746.79 148.03 -50.2, 24.6, 38.5 -901173.21 0.000 -900941.16 7 Pd(O2)(Cl)(κ1-NA-NBH) with N2H in the axial position (CSS) -901028.20 265.52 -900749.49 144.92 33.9, 62.0, 87.4 -901179.40 0.000 -900945.79 8TS TS protonation of Pd(O2)(Cl)(NA-NBH) by NBH -901023.74 263.15 -900747.81 140.59 -904.4, 51.0, 83.7 -901174.49 0.000 -900942.36 9 Pd(Sp)(OOH)(Cl) - OOH cis to N2 (CSS) -901050.64 265.42 -900772.08 143.46 42.1, 49.1, 76.4 -901201.99 0.000 -900968.09
S15
Label Description Total E ZPE H S Frequencies (cm-1) Esol s2 Gsol A Pd(Npy-Nox)(H)(Cl) w/ H cis to Nox -679705.50 102.31 -679594.86 113.77 51.4, 63.1, 89.6 -679801.81 0.000 -679803.71 A_HAATS TS for HAA from Pd(Npy-Nox)(H)(Cl) w/ H cis to Nox -774021.19 102.53 -773908.11 137.46 -1607.7, 18.7, 33.4 -774144.29 2.024 -774144.16 BTS TS for κ2-κ1 isomerization Pd(κ1-Nox-Npy)(H)(Cl) -679687.86 100.86 -679578.52 118.25 -111.4, 18.1, 51.7 -679784.35 0.000 -679786.24 C Pd(κ1-Nox-Npy)(H)(Cl) w/ H cis to Npy -679688.03 101.09 -679578.08 120.22 23.5, 51.3, 60.2 -679785.18 0.000 -679787.07 DTS TS for deprotonation of Pd-H by Npy -679684.42 99.96 -679576.17 114.58 -735.3, 47.4, 63.2 -679784.48 0.000 -679786.37 E Pd(κ1-Nox-NpyH)(Cl) -679685.75 102.75 -679574.63 115.03 46.3, 57.5, 81.3 -679785.58 0.000 -679787.47 F Pd(Npy-Nox)(H)(Cl) w/ H cis to Npy -679703.39 102.23 -679592.78 114.63 46.3, 55.9, 82.5 -679799.72 0.000 -679725.17 F_HAATS TS for HAA from Pd(Npy-Nox)(H)(Cl) w/ H cis to Npy -774019.72 102.66 -773906.61 134.52 -1583.5, 31.1, 49.8 -774143.16 2.023 -774072.05 GTS TS for κ2- κ1 isomerization Pd(κ1-Npy-Nox)(H)(Cl) -679683.58 100.68 -679574.36 118.00 -194.1, 33.5, 52.6 -679780.22 0.000 -679708.08 H Pd(κ1-Npy-Nox)(H)(Cl) w/ H cis to Nox -679683.59 100.91 -679573.78 121.13 19.9, 51.5, 59.5 -679780.86 0.000 -679709.06 ITS TS for deprotonation by Nox from Pd(κ1-Npy-Nox)(H)(Cl) -679681.40 99.83 -679573.21 116.65 -538.8, 28.8, 49.8 -679781.80 0.000 -679710.28 J Pd(κ1-Npy-NoxH)(Cl) -679682.86 102.45 -679571.91 116.93 35.0, 59.5, 70.1 -679783.52 0.000 -679709.32 K (phen)Pd(H)(Cl) -728173.67 114.74 -728050.32 113.65 54.7, 89.6, 97.9 -728275.30 0.000 -728187.73 K_HAATS TS for HAA from (phen)Pd(H)(Cl) -822489.78 115.08 -822363.99 133.84 -1578.4, 34.1, 51.8 -822618.54 2.022 -822534.55 LTS TS for κ2- κ1 isomerization -728148.18 112.80 -728026.43 119.49 -265.9, 22.9, 56.1 -728250.58 0.000 -728166.35 M Pd(κ1-phen)(H)(Cl) -728148.45 112.82 -728026.27 123.37 16.5, 40.1, 69.3 -728252.05 0.000 -728168.54 NTS TS for deprotonation of Pd(η1-phen)(H)(Cl) -728148.25 112.58 -728027.08 115.78 -95.5, 27.6, 75.8 -728253.36 0.000 -728168.61 O Pd(κ1-phenH)(Cl) -728149.50 114.22 -728026.44 117.82 31.4, 57.0, 76.0 -728255.62 0.000 -728169.58 P (bpy)Pd(H)(Cl) -680336.28 106.61 -680221.40 112.19 52.5, 75.2, 93.2 -680429.64 0.000 -680350.11 P_HAATS TS for HAA from (bpy)Pd(H)(Cl) -774652.26 106.94 -774534.94 132.76 -1587.1, 26.4, 56.6 -774772.81 2.021 -774696.96
QTS TS for κ2- κ1 isomerization Pd(κ1-bpy)(H)(Cl) w/ H cis to associated N -680316.55 105.05 -680203.06 115.55 -65.0, 31.4, 48.6 -680407.07 0.000 -680329.92
R Pd(κ1-bpy)(H)(Cl) w/ H cis to the associated N -680321.22 105.51 -680207.04 116.62 43.8, 52.5, 73.2 -680412.17 0.000 -680334.65 STS TS for swing of the hydride -680315.31 104.94 -680201.84 116.90 -254.3, 37.7,49.4 -680407.10 0.000 -680330.38 T Pd(κ1-bpy)(H)(Cl) with H cis to the dissociated arm -680318.18 105.05 -680204.20 119.77 30.0, 51.4, 69.7 -680408.83 0.000 -680332.44 UTS TS for deprotonation of Pd(κ1-bpy)(H)(Cl) -680310.88 104.33 -680198.34 113.44 -291.6, 42.0, 55.8 -680407.69 0.000 -680330.87 V Pd(κ1-bpyH)(Cl) -680311.59 106.09 -680197.02 116.17 38.3, 47.4, 64.8 -680409.05 0.000 -680331.01
Npy-Nox = 2-(4,5-dihydro-2-oxazolyl)-pyridine phen = 1,10-phenanthroline bpy = 2,2’-bipyridine
S16
Npy-Nox = 2-(4,5-dihydro-2-oxazolyl)-pyridine phen = 1,10-phenanthroline bpy = 2,2’-bipyridine
Label Description Total E ZPE H S Frequencies (cm-1) Esol s2 Gsol W Pd(Npy-Nox )(H)(OAc) H cis to ox -534288.32 133.56 -534144.01 136.10 26.9, 31.4, 40.7 -534403.24 0.000 -534301.40 W_RETS TS for R.E. from Pd( Npy-Nox )(H)(OAc) -534279.14 131.66 -534136.76 137.75 -814.7, 25.1, 26.9 -534392.45 0.000 -534293.04 W_HAATS TS for HAA from Pd( Npy-Nox )(H)(OAc) -628607.79 134.17 -628460.78 157.44 -1494.2,22.2,24.53 -628748.32 2.025 -628650.13 X Pd(phen)(H)(OAc) -582756.56 145.99 -582599.57 134.96 26.5, 37.0, 47.8 -582876.79 0.000 -582761.93 X_RETS TS for R.E. from Pd(phen)(H)(OAc) -582744.58 143.95 -582589.60 136.07 -828.3, 23.0, 38.6 -582863.20 0.000 -582750.68 X_HAATS TS for HAA from Pd(phen)(H)(OAc) -677075.59 146.61 -676915.93 154.23 -1470.8, 24.5, 28.2 -677221.77 2.023 -677110.00 Y Pd(bpy)(H)(OAc) -534919.26 137.95 -534770.65 133.91 22.7, 36.1, 49.5 -535031.23 0.000 -534924.44 Y_RETS TS for R.E. from Pd(bpy)(H)(OAc) -534906.97 135.83 -534760.48 133.85 -898.8, 26.8, 45.6 -535017.00 0.000 -534912.30 Y_HAATS TS for HAA from Pd(bpy)(H)(OAc) -629237.71 138.49 -629086.50 154.88 -1469.6, 11.1, 22.0 -629375.63 2.023 -629272.49 Z Pd(Sp)(H)(OAc) -661279.11 290.89 -660974.39 154.03 11.8, 22.1, 43.5 -661419.01 0.000 -661162.10 Z_RETS TS for R.E. from Pd(Sp)(H)(OAc) -661266.48 288.26 -660964.33 152.43 -778.5, 30.9, 45.1 -661404.11 0.000 -661149.29 Z_HAATS TS for HAA from Pd(Sp)(H)(OAc) -755597.44 291.23 -755290.29 171.21 -1472.2, 22.7, 32.1 -755763.36 2.024 -755509.15
S17
Cartesian Coordinates for Optimized Complexes O2 O 0.0000000 0.0000000 0.6028760 O 0.0000000 0.0000000 -0.6028760 1 C 4.381832 1.272288 -3.286962 C 2.876019 1.464447 -3.499609 N 2.050294 1.386364 -2.258120 C 2.345906 0.132480 -1.486400 C 3.856482 -0.149792 -1.293511 C 4.640836 -0.077583 -2.609259 C 2.175696 2.632026 -1.458874 C 1.451438 2.577259 -0.101699 C 1.979565 1.375994 0.692498 C 1.608893 0.128077 -0.123240 C -0.090888 2.505109 -0.131606 N -0.598109 1.242386 -0.774803 C 0.072764 0.037883 -0.191964 C -2.068629 1.134097 -0.503499 C -2.868261 2.332163 -1.019078 C -2.301760 3.663114 -0.505201 C -0.785575 3.728468 -0.741858 Pd -0.176937 1.170235 -2.907328 Cl 0.095238 1.037547 -5.213255 H -0.248654 -0.826553 -0.780429 H -0.296175 -0.102643 0.839253 H 3.060395 1.454025 0.849852 H 1.516752 1.333690 1.687420 H 1.940907 -0.680113 -2.104900 H 3.232852 2.863171 -1.251720 H 1.787093 3.446164 -2.078917 H 1.935309 -0.778162 0.404687 H 1.697876 3.510892 0.422187 H -0.399130 2.454195 0.930189 H -2.418088 0.207618 -0.966148 H -2.201697 1.042340 0.588916 H 2.504517 0.694178 -4.180452 H 2.650759 2.421279 -3.978907 H -0.365524 4.633498 -0.282795 H -0.576567 3.773952 -1.818043 H -2.857580 2.322088 -2.113728 H -3.911624 2.208071 -0.700861 H -2.503626 3.765258 0.571805 H -2.802280 4.503727 -1.000709 H 3.957556 -1.144657 -0.838683 H 4.296719 0.562031 -0.583683 H 5.711068 -0.228205 -2.418764 H 4.319823 -0.888245 -3.279714 H 4.873944 1.319608 -4.266852 H 4.811703 2.084339 -2.682768 H -1.647772 0.950354 -3.284019
2TS C 0.114180 -1.367790 -1.721200 C 1.587665 -1.483755 -1.276303 C 0.861600 -2.021645 1.004701 C -0.622501 -1.968902 0.576531 H -0.010871 -0.577644 -2.466676 H -0.145396 -2.326143 -2.203803 C 1.685216 -2.549663 -0.176412 H 2.725178 -2.724434 0.121422 H 1.289088 -3.510890 -0.532111 C 2.258933 -0.171215 -0.811565 H 1.990369 0.617194 -1.534600 C 1.518536 -0.728966 1.521825 H 2.464712 -1.033165 2.014608 H 0.899566 -0.269241 2.302676 H 2.130039 -1.817303 -2.171733 H 0.894632 -2.743365 1.832806 N 1.718830 0.273713 0.480918 N -0.891374 -1.115084 -0.637118 H -0.851606 -3.007559 0.268082 C -2.247429 -1.487941 -1.154225 H -2.417266 -0.936749 -2.084265 H -2.257112 -2.565875 -1.394265 C 2.341994 1.514418 0.953252 H 2.056655 2.319816 0.260415 H 1.902358 1.770356 1.923900 C -1.616684 -1.610405 1.687403 H -1.396366 -2.221521 2.572528 H -1.483186 -0.559064 1.975454 C -3.337876 -1.171844 -0.123286 H -3.422685 -0.079635 0.019619 H -4.307997 -1.484883 -0.529629 C -3.062661 -1.856482 1.224019 H -3.225768 -2.938862 1.115983 H -3.773981 -1.503887 1.980199 C 3.805675 -0.271158 -0.823296 H 4.146489 -0.505864 -1.841689 H 4.139828 -1.095917 -0.179162 C 4.449373 1.037436 -0.335231 H 5.540472 0.928588 -0.286134 H 4.245666 1.836699 -1.064290 C 3.876902 1.446009 1.030870 H 4.273165 2.421889 1.341639 H 4.186688 0.719792 1.796530 Pd -1.326830 1.031936 -0.257139 Cl -2.004120 3.193529 0.045488 H 0.041820 1.569613 -0.551506
S18
3 C 0.073954 -1.431465 -1.719635 C 1.550442 -1.476924 -1.265679 C 0.827465 -2.014049 1.014369 C -0.659236 -1.995084 0.571187 H -0.073995 -0.682261 -2.501510 H -0.143452 -2.423929 -2.157622 C 1.684305 -2.522451 -0.150221 H 2.727177 -2.662996 0.157424 H 1.321698 -3.497247 -0.499802 C 2.192557 -0.134718 -0.833145 H 1.862471 0.652733 -1.524923 C 1.452101 -0.711984 1.549389 H 2.413837 -0.954246 2.019309 H 0.815012 -0.243663 2.306632 H 2.113170 -1.800492 -2.151780 H 0.869382 -2.726835 1.849155 N 1.660505 0.324481 0.499982 N -0.925686 -1.152723 -0.644694 H -0.860536 -3.044689 0.276856 C -2.282837 -1.507652 -1.161652 H -2.448819 -0.927428 -2.074311 H -2.288332 -2.580252 -1.435810 C 2.319656 1.572409 1.001706 H 1.968434 2.378694 0.346745 H 1.901112 1.774625 1.991521 C -1.661242 -1.638910 1.675014 H -1.431808 -2.230361 2.572322 H -1.553542 -0.575821 1.926722 C -3.382251 -1.224874 -0.134533 H -3.451902 -0.140324 0.016102 H -4.341717 -1.563061 -0.547928 C -3.098130 -1.919650 1.205907 H -3.236227 -3.006034 1.096089 H -3.816615 -1.585878 1.964293 C 3.731607 -0.191624 -0.853945 H 4.045088 -0.414914 -1.882024 H 4.095112 -1.019410 -0.230349 C 4.372290 1.118472 -0.374545 H 5.464302 1.017929 -0.360750 H 4.135332 1.926509 -1.081058 C 3.843957 1.487683 1.017188 H 4.238484 2.458888 1.340300 H 4.186037 0.748828 1.756519 Pd -1.043285 1.058451 -0.321457 Cl -0.876281 3.353224 -0.028186 H 0.546693 0.711276 0.229420
4 Cl -0.714594 -1.517741 2.189838 Pd -2.030479 -1.345725 0.198196 O -2.887392 -1.125363 -1.595499 O -1.883912 -0.882562 -2.389932 N 1.358389 -0.459124 -0.395768 C 1.220788 -1.921950 -0.774257 C 2.545649 -2.549007 -1.196320 C 3.601718 -2.380827 -0.097321 C 3.768499 -0.895035 0.249662 C 2.443783 -0.235181 0.658158 C 2.562294 1.273483 0.965459 C 1.296408 1.833056 1.640158 N 0.128522 1.819015 0.747877 C 0.372590 2.541580 -0.515492 C 1.613131 1.931833 -1.217321 C 1.457710 0.448329 -1.601300 C 2.841080 2.087290 -0.308423 C -0.879232 2.547866 -1.407844 C -2.099976 3.106104 -0.666050 C -2.317809 2.313048 0.626565 C -1.053414 2.305426 1.482354 H -1.187693 1.648664 2.347705 H -0.858598 3.330351 1.860974 H -2.592150 1.275419 0.386415 H -3.141352 2.736951 1.214969 H -1.939442 4.169338 -0.429473 H -2.986390 3.052035 -1.309403 H -0.661744 3.144383 -2.304527 H -1.112569 1.530073 -1.742551 H 0.628329 3.601535 -0.294289 H 1.513662 2.864752 1.985072 H 1.041985 1.236393 2.523069 H 3.392032 1.379905 1.676537 H 0.475527 -0.184257 0.087911 H 2.985746 3.143105 -0.048069 H 3.756213 1.757416 -0.815167 H 1.766121 2.478183 -2.157584 H 0.553852 0.259669 -2.184504 H 2.320786 0.124503 -2.189131 H 0.455781 -1.967869 -1.552842 H 0.821473 -2.408163 0.120213 H 2.907273 -2.116797 -2.139610 H 2.355730 -3.610020 -1.397110 H 4.562434 -2.801014 -0.417466 H 3.290190 -2.936996 0.797458 H 4.461831 -0.772862 1.090993 H 4.221056 -0.370748 -0.601741 H 2.042772 -0.750942 1.538398
S19
MECP Pd -1.788892 -1.677368 0.016965 N -0.296054 1.699251 0.841206 C -1.650965 1.972695 1.357895 C -2.653444 2.319557 0.256506 C -2.138228 3.479090 -0.602407 C -0.744513 3.131140 -1.138980 C 0.227092 2.797834 0.004761 C 1.651512 2.443142 -0.491121 C 2.576782 2.247778 0.719646 C 2.030578 1.046856 1.507679 C 2.112801 -0.255019 0.683657 N 1.358546 -0.071695 -0.639308 C 1.720738 1.190435 -1.383610 C 3.544554 -0.750626 0.437282 C 3.584084 -2.022850 -0.420151 C 2.857853 -1.785599 -1.749880 C 1.427530 -1.314480 -1.507042 Cl -0.450927 -2.657385 1.698449 O -1.461081 -0.623589 -1.841837 O -2.751450 -0.704465 -1.503656 H 0.854641 -2.073128 -0.966859 H 0.889295 -1.083896 -2.427794 H 2.801208 -2.710934 -2.335492 H 3.096739 -2.845307 0.119705 H 4.623383 -2.322685 -0.598662 H 3.413253 -1.064075 -2.365679 H 3.990823 -0.940319 1.420965 H 4.156731 0.028090 -0.036351 H 2.733526 1.067204 -1.774334 H 1.544740 -1.043674 1.191947 H 1.031127 1.247295 -2.228614 H 2.631245 0.875918 2.410172 H 3.616795 2.097259 0.405808 H 2.562701 3.144470 1.351502 H 2.004915 3.279691 -1.108759 H 0.641823 2.207794 2.687087 H 0.165815 0.505608 2.486143 C 0.595994 1.367664 1.964579 H 0.335827 3.715531 0.623614 H -0.327812 3.966057 -1.719199 H -0.837858 2.270554 -1.813174 H -1.977815 1.078468 1.899158 H -1.603040 2.805843 2.089546 H -2.084714 4.400370 -0.002215 H -2.824649 3.679540 -1.434061 H -3.611646 2.577465 0.725630 H -2.825888 1.438311 -0.371130 H 0.362193 0.058876 -0.365190
5 Pd 0.144786 0.735171 -1.171247 N -0.173834 -0.061459 2.497085 C 1.300125 -0.079209 2.425371 C 1.852358 -1.357771 1.794173 C 1.315999 -2.595530 2.521126 C -0.216329 -2.544100 2.540240 C -0.723338 -1.245421 3.187893 C -2.269813 -1.154545 3.236651 C -2.682195 0.117155 3.993052 C -2.151926 1.309314 3.181643 C -2.816917 1.387836 1.791166 N -2.612016 0.065013 1.042083 C -2.951230 -1.160236 1.856125 C -4.302498 1.772968 1.837059 C -4.945164 1.801661 0.444181 C -4.757669 0.447484 -0.250747 C -3.279610 0.076796 -0.320503 Cl -0.588479 2.914515 -0.693931 O -0.664310 -1.098606 -1.053833 O 0.639169 -1.204480 -1.452811 H -2.724398 0.814043 -0.905868 H -3.099548 -0.903497 -0.765111 H -5.134227 0.480403 -1.279973 H -4.478682 2.590300 -0.160734 H -6.010619 2.046504 0.527601 H -5.338036 -0.330128 0.265320 H -4.361683 2.763366 2.304496 H -4.866132 1.090165 2.486072 H -4.037240 -1.193209 1.975818 H -2.278432 2.114688 1.172089 H -2.645867 -2.014685 1.248621 H -2.390705 2.253271 3.688327 H -3.769192 0.162600 4.132721 H -2.233821 0.121090 4.994306 H -2.635972 -2.045693 3.763890 H -0.207752 1.318754 4.122411 H -0.217253 2.021418 2.488990 C -0.619035 1.204464 3.098584 H -0.382158 -1.248108 4.246755 H -0.632084 -3.396405 3.095476 H -0.574814 -2.610950 1.505458 H 1.608356 0.795653 1.842466 H 1.717184 0.040561 3.447092 H 1.698557 -2.626657 3.553148 H 1.656886 -3.512802 2.025844 H 2.948644 -1.323746 1.841398 H 1.569830 -1.395654 0.735342 H -1.584839 -0.001089 0.879671
S20
6TS Pd -1.079367 -1.566066 0.020204 N -0.944661 1.340929 0.707563 C -2.312069 1.343780 1.276600 C -3.379895 1.005404 0.235644 C -3.283300 1.938418 -0.978779 C -1.848322 1.951283 -1.524890 C -0.840370 2.298863 -0.418739 C 0.620961 2.422922 -0.918951 C 1.506174 2.906998 0.236988 C 1.469488 1.806775 1.308456 C 2.130693 0.508573 0.796723 N 1.474291 0.063433 -0.507355 C 1.239122 1.150463 -1.525708 C 3.654908 0.622763 0.643266 C 4.295377 -0.648853 0.069338 C 3.637331 -1.013323 -1.267379 C 2.131432 -1.170467 -1.095921 Cl -0.430745 -1.981595 2.250351 O -0.766278 -2.629328 -1.651074 O -1.309656 -1.413724 -1.986803 H 1.899874 -1.977907 -0.396014 H 1.600661 -1.391899 -2.024488 H 4.027524 -1.962563 -1.651764 H 4.170287 -1.479814 0.777379 H 5.372919 -0.498478 -0.058854 H 3.871173 -0.253556 -2.025916 H 4.064230 0.840918 1.637197 H 3.917001 1.476849 0.006987 H 2.202288 1.393921 -1.982650 H 1.895146 -0.309018 1.489333 H 0.596242 0.698752 -2.286735 H 2.053478 2.112522 2.186059 H 2.525802 3.120194 -0.104029 H 1.108094 3.842361 0.650469 H 0.615193 3.166015 -1.727487 H -0.272705 2.558254 2.314852 H -0.048538 0.803022 2.508067 C 0.017321 1.627071 1.789989 H -1.103680 3.311267 -0.042969 H -1.752423 2.694205 -2.329117 H -1.617285 0.969128 -1.951467 H -2.328726 0.620149 2.097499 H -2.521552 2.343678 1.709306 H -3.573307 2.959003 -0.682348 H -3.982818 1.623682 -1.762154 H -4.367586 1.078628 0.707062 H -3.255742 -0.037479 -0.088281 H 0.512150 -0.278054 -0.230483
7 C 3.601792 1.653187 1.107903 C 2.088846 1.713132 0.934567 N 1.509502 0.406035 0.443363 C 2.184969 -0.121914 -0.813469 C 3.715017 -0.132552 -0.666476 C 4.275267 1.219133 -0.200302 C 1.251013 -0.583534 1.549835 C 0.721830 -1.938886 1.046561 C 1.683389 -2.478550 -0.019995 C 1.601826 -1.502370 -1.202446 C -0.726872 -2.006823 0.492502 N -0.923065 -1.209949 -0.765937 C 0.158490 -1.504088 -1.757369 C -2.229311 -1.609376 -1.381327 C -3.410528 -1.357320 -0.442005 C -3.211673 -2.039669 0.919417 C -1.832882 -1.697483 1.509062 Pd -1.227858 1.069355 -0.437682 Cl -1.025870 1.518536 -2.781394 H 0.046740 -0.785347 -2.573015 H -0.013895 -2.515448 -2.164406 H 2.702770 -2.568493 0.373521 H 1.377462 -3.482087 -0.339479 H 1.904715 0.610543 -1.581193 H 2.191729 -0.744457 2.086076 H 0.543140 -0.081823 2.214388 H 2.228784 -1.858168 -2.030726 H 0.728936 -2.597067 1.925746 H -0.848790 -3.069584 0.204533 H -2.335695 -1.038951 -2.307716 H -2.176350 -2.683301 -1.638306 H 1.806461 2.457518 0.183344 H 1.546996 1.962960 1.849094 H -1.652425 -2.295401 2.413247 H -1.803465 -0.640874 1.797144 H -3.536287 -0.276133 -0.304067 H -4.322769 -1.725369 -0.929020 H -3.293253 -3.130761 0.798619 H -4.003682 -1.738272 1.615092 H 4.135628 -0.403044 -1.642781 H 4.030618 -0.915106 0.035537 H 5.361292 1.146523 -0.069462 H 4.097062 1.980668 -0.972267 H 3.945652 2.648135 1.414545 H 3.874746 0.966067 1.921260 H 0.533283 0.688537 0.105271 O -1.239079 1.567125 1.529357 O -1.258308 2.705506 0.724834
S21
8TS C 1.858294 -5.054533 0.251721 C 1.650758 -3.846842 -0.669778 N 0.491052 -4.116790 -1.603806 C 0.902570 -5.241539 -2.506048 C 1.167119 -6.520907 -1.708249 C 2.191816 -6.304627 -0.582864 C 0.146370 -2.914124 -2.417629 C 0.112695 -1.588010 -1.632873 C 1.504933 -1.361335 -1.032222 C 1.680302 -2.452606 0.024961 C -0.999001 -1.351329 -0.557963 N -0.702395 -1.975524 0.802874 C 0.733718 -2.118233 1.190025 C -1.242854 0.178611 -0.486241 C -2.143269 0.645163 0.659688 C -1.590206 0.115922 1.983507 C -1.533986 -1.405411 1.923308 Pd -1.431946 -4.725732 -0.693375 O -1.354764 -4.329764 1.294567 O -2.692066 -4.611712 0.901889 Cl -2.508450 -5.184967 -2.743748 H -0.802662 -3.121318 -2.916410 H 0.914252 -2.787220 -3.200962 H 1.609157 -0.366249 -0.583124 H 2.269518 -1.440002 -1.814930 H -1.925634 -1.839627 -0.881935 H 1.091281 -1.183104 1.641926 H 0.764261 -2.888674 1.968348 H -0.082106 -0.828854 -2.401360 H 2.688185 -2.396725 0.459143 H 2.536563 -3.797772 -1.330170 H 0.093868 -5.395505 -3.223173 H 1.809302 -4.931208 -3.054629 H -2.544597 -1.806113 1.783586 H -1.144226 -1.843860 2.846911 H 2.682259 -4.836731 0.945231 H 0.958388 -5.225067 0.854450 H 0.215353 -6.873743 -1.292142 H 1.518394 -7.296336 -2.400985 H 3.194408 -6.181209 -1.019444 H 2.237780 -7.189707 0.063115 H -1.674626 0.474583 -1.450267 H -0.279935 0.701906 -0.405673 H -2.200222 1.740454 0.663085 H -3.167422 0.272720 0.515549 H -2.228514 0.403707 2.828086 H -0.595157 0.541105 2.178825 H -1.112307 -3.162810 0.960913
9 C -2.425923 0.747767 -1.136522 N -1.442660 -0.169833 -0.465296 C -1.904638 -0.529918 0.932093 C -3.394950 -0.943765 1.015133 C -4.332640 0.055617 0.329889 C -3.878092 0.261111 -1.117594 C -1.190342 -1.363755 -1.322978 C -0.317856 -2.437533 -0.655843 C -0.973516 -2.872794 0.660341 C -1.002516 -1.625136 1.557158 C 1.146857 -2.049825 -0.374336 N 1.269162 -0.936328 0.628682 C 0.453400 -1.214528 1.849862 C 2.710701 -0.837326 1.037722 C 3.658603 -0.601210 -0.139956 C 3.467014 -1.632070 -1.258658 C 1.980243 -1.737766 -1.623521 Pd 0.431916 0.960828 -0.113014 Cl 2.171031 2.375586 0.679042 O -0.356220 2.606032 -0.867076 O -0.810845 3.454002 0.206150 H 0.499480 -0.320607 2.479620 H 0.925105 -2.040128 2.409772 H -1.975781 -3.277668 0.485916 H -0.389530 -3.670726 1.136981 H -1.793220 0.397308 1.507431 H -2.144113 -1.836790 -1.597684 H -0.733939 -0.998395 -2.247426 H -1.446312 -1.870335 2.531173 H -0.279105 -3.284307 -1.354448 H 1.597543 -2.941702 0.099888 H 2.792808 -0.018834 1.754900 H 2.969673 -1.781328 1.547873 H -2.358443 1.710277 -0.630434 H -2.062155 0.914983 -2.153647 H 1.817692 -2.535353 -2.360944 H 1.638646 -0.796652 -2.073895 H 3.495887 0.409709 -0.523526 H 4.685855 -0.632635 0.245528 H 3.828373 -2.619957 -0.934053 H 4.059148 -1.352660 -2.138503 H -3.646274 -1.042137 2.079590 H -3.551359 -1.933440 0.568239 H -5.367090 -0.307197 0.375376 H -4.306563 1.018707 0.859145 H -4.488652 1.024117 -1.616698 H -4.011080 -0.667338 -1.690893 H 0.040686 3.819665 0.522608
S22
1_HAATS C 1.441640 -1.926737 -1.820101 C 0.635227 -2.174354 -0.538856 N 0.996999 -1.157872 0.510778 C 2.451703 -1.311241 0.832895 C 3.351552 -1.117836 -0.389576 C 2.947939 -2.042601 -1.545216 C 0.208072 -1.369774 1.763476 C -1.308066 -1.529324 1.543998 C -1.532068 -2.708383 0.584660 C -0.889004 -2.303400 -0.747603 C -2.049533 -0.267219 1.035585 N -1.631967 0.082647 -0.363081 C -1.624896 -1.068865 -1.297644 C -3.581540 -0.419370 1.205901 C -4.354209 0.785057 0.653126 C -3.954288 1.029110 -0.806139 C -2.435928 1.218530 -0.903322 Pd 0.569292 0.882206 -0.134622 Cl 0.321248 3.089380 -0.834898 H 0.428606 -0.530684 2.430519 H 0.571119 -2.289209 2.254856 H -2.596148 -2.932374 0.454416 H -1.063184 -3.618051 0.982290 H -1.738813 0.590858 1.646797 H -2.652317 -1.384820 -1.541396 H -1.170621 -0.719559 -2.230160 H -1.728555 -1.761341 2.531669 H -1.023852 -3.103796 -1.487760 H 0.956443 -3.154339 -0.138176 H 2.700852 -0.588340 1.613663 H 2.600464 -2.323806 1.247936 H -2.144823 2.111980 -0.345100 H -2.109897 1.386770 -1.933358 H 1.131788 -2.661485 -2.575202 H 1.210430 -0.929351 -2.215987 H 3.301199 -0.073272 -0.716493 H 4.388372 -1.305486 -0.083526 H 3.189376 -3.085440 -1.290099 H 3.521204 -1.797500 -2.447305 H -3.790344 -0.553325 2.275899 H -3.938530 -1.327345 0.703525 H -5.434207 0.613889 0.744815 H -4.122896 1.680470 1.248451 H -4.436770 1.933123 -1.198969 H -4.296641 0.194448 -1.434475 H 2.018717 1.546325 0.447024 O 3.092844 2.159774 0.938971 O 3.576721 1.570995 1.952847
S23
A Pd 0.142298 0.005031 0.502432 N 0.277828 0.003587 2.565700 N 2.353089 0.002313 0.874088 C 3.342349 0.001874 -0.021936 C 4.688418 0.000055 0.363187 C 5.004666 -0.001379 1.722217 C 3.971192 -0.000954 2.663621 C 2.658824 0.000927 2.192052 H 3.026951 0.003007 -1.062601 H 5.465627 -0.000230 -0.394671 H 6.040639 -0.002828 2.048949 H 4.168651 -0.002057 3.730308 C 1.471652 0.001550 3.054792 O 1.598444 -0.000320 4.394595 C 0.237572 0.000847 4.937052 C -0.676093 0.003277 3.683104 H 0.135223 -0.892951 5.556177 H 0.137467 0.893655 5.557976 H -1.316020 -0.881623 3.615126 Cl 0.195764 0.006099 -1.805061 H -1.391787 0.006881 0.401893 H -1.314170 0.889671 3.617259 BTS C -1.499072 -0.005760 -0.270803 C 0.018592 0.085984 -0.028733 N 0.145305 -0.018593 1.444192 C -1.040802 0.069726 1.945361 O -2.062324 0.165273 1.057453 Pd 2.073005 -0.240206 2.185705 Cl 4.226794 -0.503797 2.866881 C -1.452461 0.080689 3.367704 N -0.491384 0.248366 4.287238 C -0.842876 0.249553 5.572895 C -2.164439 0.087890 6.008163 C -3.162191 -0.076261 5.048243 C -2.807047 -0.078646 3.698654 H 1.747116 0.611911 3.379211 H 0.449619 1.040167 -0.350853 H 0.574794 -0.720910 -0.513662 H -1.819934 -0.983353 -0.643827 H -1.902840 0.783149 -0.907471 H -3.551522 -0.203260 2.920871 H -4.200974 -0.201856 5.340769 H -2.396042 0.094221 7.069204 H -0.033257 0.386906 6.286633
A_HAATS C -0.682294 0.003114 3.667690 N 0.272082 0.003123 2.548001 C 1.465077 0.001315 3.036675 O 1.593676 -0.000058 4.375062 C 0.232697 0.001194 4.919807 Pd 0.135234 0.005134 0.462510 Cl 0.122479 0.007205 -1.847147 C 2.659762 0.000724 2.181247 N 2.371007 0.002240 0.861056 C 3.370052 0.001902 -0.023932 C 4.711779 0.000016 0.376384 C 5.011550 -0.001552 1.738976 C 3.966791 -0.001199 2.667903 H 3.071369 0.003181 -1.069091 H 5.497579 -0.000203 -0.372583 H 6.043497 -0.003030 2.078024 H 4.151663 -0.002371 3.736788 H 0.132104 -0.892407 5.539385 H 0.134221 0.894230 5.540545 H -1.325331 -0.878828 3.600149 H -1.559797 0.007138 0.403635 H -1.323656 0.886382 3.601632 O -2.859283 0.008611 0.430730 O -3.302554 0.007967 1.619196 C C -1.476921 0.038586 -0.232486 C 0.030879 -0.144485 0.018974 N 0.156313 -0.054178 1.492832 C -1.035931 -0.057067 1.987777 O -2.057145 -0.086246 1.092526 Pd 2.088190 0.007175 2.238278 Cl 4.246215 0.083724 2.956887 C -1.464201 -0.037966 3.405812 N -0.515706 -0.123094 4.350118 C -0.886677 -0.104133 5.629808 C -2.222314 -0.002746 6.038186 C -3.208522 0.081599 5.056317 C -2.830306 0.063876 3.713265 H 1.539575 -0.140904 3.630092 H 0.638225 0.630856 -0.455913 H 0.404294 -1.121939 -0.306204 H -1.924239 -0.729038 -0.866238 H -1.734269 1.030906 -0.615396 H -3.566865 0.128583 2.921223 H -4.257743 0.160838 5.327022 H -2.472715 0.008387 7.094822 H -0.082302 -0.173884 6.359000
S24
DTS C -2.816695 0.007176 3.727274 C -1.479432 -0.025675 3.306957 N -0.482341 -0.038015 4.217039 C -0.728483 -0.017225 5.527577 C -2.033934 0.015540 6.016164 C -3.088019 0.027314 5.094675 C -1.097910 -0.048451 1.893399 N 0.109033 -0.072972 1.426183 C 0.005573 -0.138022 -0.048402 C -1.501406 0.059303 -0.324209 O -2.116281 -0.051364 0.991082 Pd 1.867544 -0.087796 2.462854 Cl 3.764917 -0.099745 3.757120 H 0.747348 -0.063330 3.688179 H 0.629853 0.639444 -0.494898 H 0.380583 -1.111759 -0.380551 H -1.944741 -0.707103 -0.962489 H -1.740754 1.051844 -0.717598 H -3.611488 0.016805 2.990415 H -4.117285 0.052796 5.440931 H -2.216387 0.031376 7.085728 H 0.145966 -0.027795 6.173144 F C 3.880150 -0.001341 2.608713 C 2.546964 0.000751 2.203236 N 2.174211 0.002572 0.892792 C 3.142855 0.002318 -0.038958 C 4.499937 0.000263 0.289091 C 4.877588 -0.001597 1.631985 C 1.420669 0.001222 3.145587 N 0.206101 0.003175 2.737771 C -0.669738 0.003047 3.913796 C 0.325277 0.000861 5.106742 O 1.650005 -0.000420 4.475280 Pd 0.111825 0.005531 0.528610 H 0.217205 0.006961 -1.005466 H 2.804911 0.003807 -1.068210 H 5.239743 0.000148 -0.505109 H 5.925781 -0.003205 1.915763 H 4.115975 -0.002712 3.667371 H 0.265164 -0.892898 5.731603 H 0.267509 0.893892 5.732872 H -1.315515 -0.879920 3.886444 Cl -2.170284 0.008640 0.221034 H -1.313623 0.887438 3.888099
E O -2.117101 -0.078118 0.976166 C -1.104164 -0.059023 1.893538 N 0.116571 -0.078003 1.433283 C 0.010256 -0.164487 -0.043058 C -1.486058 0.083732 -0.323671 C -1.484240 -0.031621 3.285619 C -2.818437 -0.006209 3.731082 C -3.080784 0.017604 5.094153 C -2.020989 0.016841 6.022844 C -0.723399 -0.008531 5.540292 N -0.489190 -0.032997 4.218088 Pd 1.867603 -0.072231 2.428813 Cl 3.764463 -0.063774 3.723635 H 0.536625 -0.049688 3.819540 H 0.665298 0.577432 -0.503862 H 0.346292 -1.159783 -0.352994 H -1.941218 -0.636507 -1.005686 H -1.691160 1.102217 -0.669754 H -3.616328 -0.005324 2.997992 H -4.108692 0.037540 5.444270 H -2.203350 0.035776 7.091495 H 0.159467 -0.010447 6.171824 F_HAATS C -0.921884 0.000792 3.366322 N -0.002327 0.000094 2.223368 C 1.196047 0.000291 2.675456 O 1.374548 0.000655 4.012447 C 0.028164 -0.000603 4.595661 Pd -0.014743 -0.000116 -0.011027 Cl -2.267201 -0.000285 -0.501150 C 2.362423 0.000236 1.782053 N 2.053145 0.000056 0.456519 C 3.061011 -0.000007 -0.430915 C 4.402426 0.000122 -0.038211 C 4.716484 0.000311 1.319838 C 3.674584 0.000362 2.249909 H 0.177244 -0.000468 -1.700331 H 2.775403 -0.000162 -1.479070 H 5.177682 0.000070 -0.797791 H 5.750278 0.000411 1.652491 H 3.861404 0.000498 3.318251 H -0.053330 -0.895064 5.217000 H -0.053894 0.891885 5.219711 H -1.566095 -0.882384 3.316612 H -1.563965 0.885569 3.316967 O 0.327823 -0.000772 -2.995003 O 1.551508 -0.000644 -3.335388
S25
GTS C 0.228871 2.486991 0.144756 N 0.314070 1.139243 0.121055 Pd -1.557971 0.174799 -0.002131 H -1.098513 -0.942548 0.893711 Cl -3.622245 -0.748398 -0.222863 N 1.012917 -1.708882 0.777600 C 1.542551 -3.052546 0.503923 C 2.770546 -2.811792 -0.413030 O 2.736530 -1.376743 -0.663162 C 1.700282 -0.891060 0.086699 C 1.549077 0.584861 0.040397 C 2.703938 1.369072 -0.068733 C 2.601072 2.757639 -0.053894 C 1.334408 3.328456 0.064796 H -0.774346 2.893868 0.224506 H 1.192369 4.404103 0.088957 H 3.489796 3.377310 -0.129516 H 3.664804 0.875658 -0.157740 H 3.727278 -3.043186 0.064356 H 2.712300 -3.316057 -1.380130 H 0.761174 -3.651001 0.021574 H 1.804344 -3.544472 1.446208 ITS O 1.643402 -0.072504 4.360364 C 1.383981 0.009423 3.039021 N 0.140680 0.075856 2.712878 C -0.692416 -0.006186 3.917098 C 0.358456 0.001202 5.056200 C 2.533945 0.006314 2.122806 C 3.828394 -0.000739 2.661874 C 4.926353 -0.005704 1.809147 C 4.689734 -0.003787 0.430888 C 3.379867 0.002063 -0.033701 N 2.294955 0.005912 0.778013 Pd 0.450245 0.006257 -0.163123 Cl -1.602715 -0.009983 -1.183212 H 3.165711 0.002416 -1.096692 H 5.506707 -0.007147 -0.283939 H 5.936642 -0.010238 2.206355 H 3.952444 -0.000674 3.738461 H 0.301627 -0.860781 5.723205 H 0.360441 0.924212 5.641261 H -1.288974 -0.924032 3.886187 H -0.093080 0.057546 1.380998 H -1.375636 0.846723 3.958685
H C -1.159077 -0.123585 -0.750094 C 0.050973 -0.104470 -0.064138 N 0.150428 -0.056528 1.282208 C -1.002677 -0.042566 1.998801 C -2.257516 -0.041977 1.374351 C -2.342762 -0.085826 -0.014306 Pd 2.149002 0.127521 1.922117 Cl 4.339463 0.391538 2.473142 C -0.961769 -0.039200 3.482451 N -0.038325 -0.486853 4.236651 C -0.458161 -0.259720 5.625699 C -1.893125 0.316288 5.508675 O -2.084065 0.474226 4.073794 H 1.787158 -0.360323 3.298704 H 0.992008 -0.122463 -0.605937 H -1.160172 -0.161929 -1.834659 H -3.310355 -0.092483 -0.507371 H -3.147735 -0.012017 1.990865 H -2.669071 -0.362643 5.874154 H -2.020037 1.299091 5.967990 H 0.243818 0.434330 6.102102 H -0.421111 -1.202601 6.180500 J N 2.282472 0.014374 0.778445 C 2.539901 0.005468 2.130357 C 3.844631 -0.013127 2.665011 C 4.932380 -0.022404 1.810229 C 4.681854 -0.011621 0.426702 C 3.376000 0.006910 -0.034798 C 1.414610 0.006600 3.040076 O 1.630279 -0.088570 4.359608 C 0.338417 0.036048 5.037877 C -0.706330 -0.058288 3.903267 N 0.148602 0.081812 2.724030 Pd 0.465574 0.043655 -0.158489 Cl -1.621531 0.053604 -1.115289 H 3.158826 0.015132 -1.096361 H 5.495784 -0.017450 -0.291793 H 5.946054 -0.035882 2.197970 H 3.973534 -0.017697 3.741545 H 0.279827 -0.770121 5.769851 H 0.334401 1.004091 5.545506 H -1.227758 -1.021291 3.874275 H -0.125589 0.089507 1.664614 H -1.448187 0.743610 3.937425
S26
K C 2.545249 -2.840523 0.414598 C 2.595610 -1.434927 0.277449 C 1.381538 -0.757472 0.002644 N 0.187173 -1.414932 -0.130525 C 0.172921 -2.743414 0.004712 C 1.332645 -3.490536 0.277582 C 1.385629 0.675869 -0.145130 C 2.596568 1.399702 -0.015981 C 3.810819 0.684321 0.262737 C 3.808956 -0.673526 0.403059 N 0.198760 1.281850 -0.407899 C 0.156134 2.600314 -0.551557 C 1.310121 3.403044 -0.440176 C 2.527971 2.803988 -0.172923 Pd -1.434090 -0.180828 -0.531280 H 1.256571 -4.568674 0.376471 H 3.456171 -3.394961 0.625566 H 1.228024 4.478144 -0.565285 H 3.433452 3.399095 -0.081924 H -0.792463 -3.221842 -0.108439 H -0.826569 3.016898 -0.760267 H 4.736086 1.246488 0.360453 H 4.732654 -1.206266 0.613905 H -2.491783 -1.301617 -0.593056 Cl -3.148888 1.303763 -0.972728 LTS C 2.491225 2.713048 -0.191434 C 2.547298 1.313619 -0.024062 C 1.345849 0.549332 -0.151820 N 0.155696 1.171485 -0.423126 C 0.147390 2.502781 -0.577975 C 1.282478 3.315392 -0.471607 C 3.797372 0.674359 0.276516 C 3.874052 -0.671685 0.451386 C 2.701483 -1.486144 0.329850 C 1.435374 -0.901202 0.021968 N 0.333144 -1.665257 -0.109501 C 0.408768 -2.974505 0.059229 C 1.608055 -3.643502 0.377138 C 2.755950 -2.888056 0.506725 Pd -1.848276 0.468476 -0.629874 Cl -4.050124 -0.056772 -0.881044 H 1.617667 -4.721258 0.509055 H 3.709109 -3.354978 0.743922 H 1.191462 4.387654 -0.610731 H 3.402716 3.297741 -0.096795 H -0.521250 -3.527368 -0.062827 H -0.816712 2.951118 -0.803347 H 4.682984 1.298342 0.364561 H 4.822153 -1.150492 0.683700 H -1.429033 -0.924977 -0.981537
K_HAATS C 2.538111 2.807278 -0.171598 C 2.605653 1.402709 -0.014767 C 1.394076 0.679008 -0.143815 N 0.209808 1.287863 -0.406256 C 0.166822 2.606239 -0.550024 C 1.321507 3.408236 -0.438669 C 3.819987 0.687941 0.263718 C 3.818084 -0.669900 0.404030 C 2.604806 -1.430759 0.278549 C 1.390257 -0.754767 0.004028 N 0.198684 -1.415442 -0.128185 C 0.182761 -2.742708 0.006627 C 1.344990 -3.488741 0.279599 C 2.555736 -2.837026 0.415947 Pd -1.446591 -0.177158 -0.533568 Cl -3.211755 1.248256 -0.978532 H 1.268936 -4.566813 0.378470 H 3.467995 -3.389429 0.626767 H 1.240011 4.483375 -0.563733 H 3.444276 3.401305 -0.080547 H -0.783551 -3.226817 -0.105911 H -0.813638 3.027064 -0.758684 H 4.745052 1.250383 0.361223 H 4.741688 -1.202780 0.614733 H -2.613652 -1.420741 -0.601497 O -3.492753 -2.376274 -0.650895 O -2.969640 -3.516139 -0.443905 M C 2.771659 -2.883866 0.494682 C 2.712735 -1.481174 0.325658 C 1.441889 -0.890272 0.047538 N 0.342419 -1.666273 -0.044529 C 0.415484 -2.976345 0.116658 C 1.624035 -3.644143 0.391361 C 1.353761 0.562005 -0.133880 C 2.561528 1.318823 -0.016689 C 3.813272 0.674757 0.265496 C 3.890219 -0.671886 0.430016 N 0.167340 1.193973 -0.406976 C 0.168319 2.526876 -0.557043 C 1.309237 3.330116 -0.454648 C 2.515435 2.718801 -0.182631 Pd -1.797548 0.465242 -0.665941 Cl -3.962198 -0.195044 -0.967852 H 1.640515 -4.722426 0.516340 H 3.731566 -3.349050 0.706288 H 1.224898 4.403468 -0.589734 H 3.432134 3.295952 -0.093615 H -0.521550 -3.522536 0.024927 H -0.794513 2.981918 -0.771356 H 4.701390 1.296416 0.343739 H 4.840344 -1.155404 0.642858 H -1.256064 -0.915889 -0.395264
S27
NTS N 0.024503 0.006913 0.036277 H 0.128383 0.008105 1.519285 Pd 0.979607 -0.008954 2.829997 Cl -0.725492 0.035327 4.362331 N 2.540235 -0.049522 1.437916 C 2.471479 -0.051477 0.066335 C 1.192443 -0.022816 -0.641246 C 1.169645 -0.026078 -2.067871 C 2.394875 -0.057297 -2.810248 C 3.588605 -0.084028 -2.160198 C 3.659916 -0.081905 -0.725431 C 4.912212 -0.110026 -0.077436 C 4.957801 -0.107442 1.302892 C 3.753488 -0.076883 2.014147 C -1.148869 0.033304 -0.573776 C -1.256011 0.032097 -1.974871 C -0.087634 0.002213 -2.713878 H -2.022758 0.055920 0.073854 H -2.231294 0.054109 -2.450569 H -0.119473 0.000061 -3.800694 H 2.349306 -0.059113 -3.896204 H 4.521864 -0.107768 -2.716885 H 5.821509 -0.133276 -0.672175 H 5.898050 -0.128397 1.844435 H 3.759951 -0.074176 3.099058 P Pd 2.416392 -2.696357 0.400687 N 2.590325 -0.530039 0.210576 C 1.416414 0.090820 -0.043926 C 1.361444 1.482734 -0.194040 C 2.536110 2.225616 -0.077440 C 3.738141 1.567402 0.185643 C 3.719574 0.179054 0.323153 C 0.231934 -0.800233 -0.146985 C -1.059226 -0.323686 -0.405571 C -2.125721 -1.215271 -0.489200 C -1.879318 -2.576988 -0.311377 C -0.575362 -2.991873 -0.057064 N 0.459812 -2.133376 0.024811 H 2.158693 -4.214925 0.511497 Cl 4.638824 -3.180509 0.811349 H 4.612404 -0.406945 0.528116 H 4.672481 2.111025 0.283223 H 2.508916 3.305714 -0.191421 H -0.328104 -4.035854 0.088654 H -2.676171 -3.311600 -0.366890 H -3.129301 -0.851497 -0.689493 H 0.423938 1.987316 -0.398504 H -1.232409 0.737511 -0.541144
O C 2.665003 -2.865480 0.477654 C 2.662215 -1.464609 0.317458 C 1.423607 -0.817766 0.034493 N 0.311338 -1.593942 -0.064894 C 0.307246 -2.917985 0.085336 C 1.491080 -3.601724 0.363286 C 1.347859 0.615250 -0.141731 C 2.567150 1.352083 -0.019849 C 3.801584 0.672789 0.266123 C 3.855223 -0.676760 0.429112 N 0.148092 1.236367 -0.415219 C 0.167997 2.579024 -0.564951 C 1.319533 3.360163 -0.459578 C 2.533696 2.747946 -0.184713 Pd -1.711779 0.365874 -0.631044 Cl -3.739814 -0.696782 -0.855958 H 1.481880 -4.679445 0.484598 H 3.605460 -3.365980 0.693575 H 1.244829 4.434599 -0.594715 H 3.450443 3.324183 -0.095614 H -0.660103 -3.400298 -0.023130 H -0.790814 3.036777 -0.779044 H 4.703913 1.273089 0.350048 H 4.794752 -1.177894 0.644946 H -0.654085 -1.045440 -0.290789 P_HAATS N 0.449416 -2.118776 0.021549 C 0.225299 -0.785737 -0.149605 C -1.064344 -0.306984 -0.408160 C -2.132056 -1.198419 -0.492165 C -1.887922 -2.559535 -0.314913 C -0.583364 -2.977465 -0.060070 C 1.411337 0.103981 -0.046141 N 2.584723 -0.515679 0.207693 C 3.715643 0.190656 0.320693 C 3.735908 1.579026 0.183786 C 2.534191 2.237874 -0.078622 C 1.358691 1.496213 -0.195321 Pd 2.423139 -2.698232 0.401774 Cl 4.629507 -3.254913 0.817619 H 2.142815 -4.381184 0.526046 H 4.609647 -0.392714 0.525324 H 4.671048 2.121190 0.281455 H 2.507714 3.317996 -0.192018 H -0.343338 -4.026958 0.085042 H -2.684719 -3.294091 -0.370603 H -3.134996 -0.832719 -0.692571 H 0.421866 2.002160 -0.399112 H -1.237448 0.754244 -0.543549 O 1.923389 -5.657526 0.619180 O 0.696692 -5.944464 0.448208
S28
QTS C -0.102534 0.242877 -0.004342 N -0.079329 0.224566 1.344493 Pd 1.558877 0.781024 2.509230 H 2.212079 1.566675 1.391229 Cl 3.300807 1.363671 3.850399 N -0.599875 -1.361763 4.049897 C -0.495846 -1.420053 5.384204 C -0.865678 -0.372456 6.232015 C -1.365303 0.799039 5.663249 C -1.476059 0.877565 4.273902 C -1.080077 -0.228387 3.510153 C -1.174695 -0.208532 2.011933 C -2.321825 -0.632113 1.339970 C -2.344600 -0.611864 -0.054718 C -1.212254 -0.166215 -0.737609 H 0.800479 0.595239 -0.488415 H -1.179742 -0.133776 -1.821951 H -3.227219 -0.940060 -0.596390 H -3.175614 -0.978698 1.913381 H -1.844501 1.776430 3.788513 H -1.653908 1.641166 6.285959 H -0.753780 -0.473994 7.307324 H -0.093941 -2.346860 5.787616 STS C -0.057013 0.414386 0.031416 N -0.031989 0.324363 1.382002 Pd 1.958076 0.317589 2.105043 H 1.702187 0.925525 3.458894 N -1.827296 -1.110411 4.058213 C -1.927168 -1.168179 5.391291 C -1.462356 -0.162534 6.243278 C -0.874885 0.967333 5.673194 C -0.751855 1.035114 4.285555 C -1.225112 -0.037988 3.517219 C -1.176100 -0.015027 2.026143 C -2.340733 -0.332706 1.311584 C -2.349716 -0.259234 -0.076839 C -1.182975 0.139234 -0.733284 Cl 4.151857 0.200105 2.669429 H 0.876723 0.708730 -0.440152 H -1.135234 0.227896 -1.813790 H -3.249870 -0.498528 -0.635986 H -3.221181 -0.631219 1.868998 H -2.405048 -2.059404 5.793089 H -1.569652 -0.262134 7.319370 H -0.517961 1.783609 6.295135 H -0.314922 1.903993 3.806115
R C -1.209634 0.169605 -0.735787 C -0.115002 0.501880 0.055164 N -0.141986 0.434093 1.402912 C -1.286762 0.033324 2.013849 C -2.416969 -0.336405 1.275868 C -2.381951 -0.265459 -0.113597 Pd 1.553272 0.811150 2.578872 Cl 3.366140 1.234054 3.902349 C -1.298832 -0.023328 3.501287 N -2.062765 -0.985086 4.048047 C -2.060312 -1.109926 5.378749 C -1.300992 -0.301593 6.232444 C -0.535835 0.716806 5.667903 C -0.547745 0.872942 4.280296 H 2.548147 0.678494 1.439020 H 0.821792 0.824914 -0.382198 H -1.132609 0.244906 -1.815707 H -3.253003 -0.542158 -0.700836 H -3.296844 -0.674795 1.810639 H -2.690763 -1.900257 5.781441 H -1.321450 -0.465542 7.305581 H 0.058252 1.384078 6.285175 H -0.044715 1.735110 3.830337 T H -0.857351 -1.359318 0.266316 N -0.009458 0.255832 4.085477 C 1.293384 0.252146 4.381677 C 2.282025 0.728050 3.514746 C 1.883125 1.247174 2.283732 C 0.525964 1.253282 1.960402 C -0.389634 0.728945 2.883714 C -1.861233 0.702789 2.638096 C -2.728282 0.917495 3.721302 C -4.104049 0.919951 3.525615 C -4.599296 0.699581 2.238370 C -3.692023 0.473063 1.211824 N -2.350760 0.471959 1.393148 Pd -1.261577 -0.033304 -0.340122 Cl -0.186762 -0.551680 -2.270257 H -4.030631 0.266016 0.202159 H -5.663796 0.688630 2.027744 H -4.778129 1.091644 4.360171 H -2.293634 1.076545 4.700819 H 1.557542 -0.150663 5.357577 H 3.328275 0.696378 3.804319 H 2.611780 1.641922 1.581333 H 0.189403 1.658672 1.012626
S29
UTS H -0.516653 -0.891153 0.428568 N 0.652671 -1.484117 0.458157 C 0.728058 -2.821448 0.441806 C 1.881429 -3.478100 0.027460 C 2.960555 -2.700932 -0.406910 C 2.857452 -1.310978 -0.399897 C 1.674591 -0.703572 0.050287 C 1.502275 0.775756 0.069702 C 2.634978 1.589739 0.234041 C 2.514137 2.974196 0.206892 C 1.244578 3.523065 0.009999 C 0.159749 2.666304 -0.124819 N 0.259075 1.314696 -0.087212 Pd -1.552014 0.291574 -0.073803 Cl -3.527351 -0.883179 0.000189 H -0.842129 3.054622 -0.266960 H 1.086758 4.596337 -0.026680 H 3.386125 3.607469 0.343288 H 3.603255 1.134984 0.412101 H -0.167527 -3.345435 0.765457 H 1.926090 -4.562372 0.030533 H 3.869716 -3.174334 -0.767623 H 3.675017 -0.705049 -0.773913 W C -2.927277 1.820589 -0.043180 C -1.904846 0.872121 -0.022537 N -0.593990 1.207095 -0.017244 C -0.254905 2.497820 -0.032314 C -1.215188 3.516447 -0.053434 C -2.567364 3.171198 -0.058896 C -2.125808 -0.579288 -0.004386 N -1.142064 -1.414009 0.014420 C -1.694103 -2.775523 0.029355 C -3.227607 -2.542139 0.012980 O -3.373744 -1.083960 -0.006812 Pd 0.744009 -0.606748 0.017616 O 2.460719 0.443191 0.016159 C 3.670703 -0.069683 0.032487 C 4.751037 1.013866 0.026364 O 3.962937 -1.262092 0.050950 H 0.813058 2.699526 -0.027041 H -0.900556 4.555350 -0.065243 H -3.334178 3.940379 -0.075161 H -3.965223 1.505125 -0.046696 H -3.739246 -2.906189 0.906458 H -3.723425 -2.928802 -0.879949 H -1.346284 -3.298184 0.925305 H 1.524088 -1.928048 0.041546 H -1.331323 -3.323867 -0.845019 H 4.636692 1.664551 0.901308 H 5.742392 0.555721 0.038106 H 4.647837 1.643850 -0.864936
V N -2.406610 -0.000657 1.467112 C -1.893183 0.777591 2.470909 C -2.727687 1.568038 3.285022 C -4.095861 1.604155 3.062894 C -4.614147 0.838596 2.010125 C -3.748804 0.063017 1.255401 C -0.432378 0.808227 2.697693 N 0.330259 -0.211769 2.234894 C 1.667867 -0.261836 2.352528 C 2.354496 0.746354 3.006406 C 1.613270 1.827951 3.507838 C 0.231764 1.863038 3.349674 Pd -1.433626 -1.450468 0.360473 Cl -0.257077 -3.083223 -0.759509 H -0.191869 -0.954565 1.551604 H -4.116531 -0.550618 0.441253 H -5.675339 0.831185 1.781938 H -4.743368 2.204119 3.694993 H -2.303914 2.128989 4.110309 H 2.141362 -1.130387 1.903995 H 3.432827 0.696726 3.111351 H 2.117846 2.652370 4.003286 H -0.327007 2.722279 3.700081 W_RETS C -3.670301 -0.654468 -0.000035 C -2.303876 -0.348833 -0.000005 N -1.339584 -1.289465 0.000036 C -1.710655 -2.569336 0.000041 C -3.049337 -2.977730 0.000012 C -4.044047 -1.999399 -0.000026 C -1.820147 1.039800 -0.000010 N -0.577911 1.380169 -0.000004 C -0.512417 2.851467 0.000004 C -1.998284 3.290983 0.000038 O -2.740362 2.036202 -0.000019 Pd 0.974283 0.031173 -0.000004 O 2.728079 -1.186098 -0.000005 C 3.754037 -0.459805 -0.000001 C 5.127051 -1.082408 -0.000005 O 3.680824 0.832523 0.000000 H -0.901415 -3.297281 0.000071 H -3.298547 -4.035028 0.000022 H -5.094782 -2.276178 -0.000048 H -4.408855 0.140781 -0.000066 H -2.293864 3.847778 -0.892699 H -2.293845 3.847684 0.892841 H 0.036170 3.187406 -0.884756 H 2.479724 0.975717 -0.000010 H 0.036204 3.187397 0.884746 H 5.050037 -2.171438 0.000057 H 5.684562 -0.749292 -0.882047 H 5.684623 -0.749186 0.881956
S30
W_HAATS O 3.873515 -0.153580 2.579546 C 2.608725 0.006243 2.154274 N 2.405590 0.024300 0.881621 C 3.701279 -0.146467 0.204127 C 4.704956 -0.267937 1.378989 C 1.517181 0.152631 3.122877 C 1.714277 0.136064 4.502738 C 0.593225 0.285332 5.325238 C -0.659045 0.442499 4.735996 C -0.767305 0.447518 3.337261 N 0.302685 0.305026 2.548083 Pd 0.466920 0.269102 0.199504 O -1.336894 0.495519 -0.706584 C -2.496673 0.647865 -0.137101 C -3.637240 0.788959 -1.139748 O 1.263705 0.148610 -2.687434 O 2.507775 -0.012166 -2.866207 H -1.709432 0.565165 2.806898 H -1.553650 0.561279 5.339619 H 0.702874 0.278103 6.406090 H 2.711586 0.010509 4.910574 H 5.440320 0.538504 1.416814 H 5.212774 -1.233469 1.428010 H 3.895018 0.714197 -0.441985 H 0.955917 0.196267 -1.399312 H 3.670139 -1.036174 -0.430849 H -3.457662 1.652135 -1.790601 H -4.587989 0.912597 -0.616240 H -3.680828 -0.097059 -1.783150 O -2.711487 0.682412 1.081807 X_RETS C -2.662161 2.927044 0.000095 C -2.813507 1.523194 0.000059 C -1.640566 0.718870 -0.000013 N -0.385863 1.268336 -0.000094 C -0.281779 2.603715 -0.000075 C -1.390048 3.466021 0.000035 C -1.780132 -0.726327 -0.000021 C -3.081115 -1.303480 0.000036 C -4.239362 -0.456128 0.000085 C -4.108537 0.900091 0.000099 N -0.654763 -1.480264 -0.000067 C -0.769422 -2.802514 -0.000050 C -2.013426 -3.470582 0.000021 C -3.170024 -2.714310 0.000060 Pd 1.298863 0.029543 -0.000080 O 3.192211 -0.994463 -0.000104 C 4.129837 -0.138038 0.000029 C 5.571360 -0.605019 0.000308 O 3.921631 1.117492 0.000004 H -1.228283 4.539534 0.000062
X C 3.434236 -2.275618 0.000354 C 3.146557 -0.891607 0.000267 C 1.784219 -0.503236 0.000054 N 0.759849 -1.414242 -0.000068 C 1.064570 -2.714710 0.000023 C 2.391040 -3.182675 0.000235 C 1.445679 0.898164 -0.000029 C 2.469756 1.877040 0.000105 C 3.841651 1.451314 0.000314 C 4.164012 0.124710 0.000392 N 0.127337 1.223440 -0.000229 C -0.230761 2.500729 -0.000300 C 0.717445 3.544815 -0.000180 C 2.065243 3.232872 0.000022 Pd -1.128078 -0.585359 -0.000348 O -2.857407 0.446158 -0.000634 C -4.063715 -0.076419 -0.000083 C -5.150995 1.000512 0.001237 O -4.348677 -1.270399 0.000190 H 2.573614 -4.252506 0.000303 H 4.468007 -2.611762 0.000521 H 0.379570 4.576398 -0.000249 H 2.818206 4.017319 0.000116 H 0.224045 -3.398158 -0.000068 H -1.301723 2.687362 -0.000459 H 4.622423 2.207663 0.000412 H 5.204983 -0.188183 0.000552 H -1.900797 -1.916317 -0.000418 H -5.041579 1.648234 -0.876471 H -6.139396 0.535900 -0.006993 H -5.051001 1.634787 0.889936 X_HAATS C 2.471632 -3.260974 -0.001893 C 2.766427 -1.876764 -0.001153 C 1.668709 -0.980135 -0.000349 N 0.377328 -1.403632 -0.000273 C 0.121795 -2.708697 -0.000972 C 1.154166 -3.672965 -0.001802 C 4.102983 -1.352302 -0.001182 C 4.330621 -0.006626 -0.000452 C 3.240191 0.928581 0.000369 C 1.909287 0.439509 0.000424 N 0.826297 1.275440 0.001185 C 1.031901 2.594791 0.001892 C 2.320776 3.159118 0.001891 C 3.425479 2.329686 0.001134 Pd -1.045236 0.363256 0.001110 O -2.990251 -0.232453 0.001185 C -3.489084 -1.433898 0.000669 C -5.014546 -1.441999 0.000632 O -2.619649 2.920789 0.003047 O -1.928279 3.985555 0.003478
S31
H -3.543865 3.563135 0.000161 H -2.044917 -4.556096 0.000051 H -4.148990 -3.188228 0.000118 H 0.729188 2.997616 -0.000177 H 0.161041 -3.363023 -0.000118 H -5.223913 -0.917802 0.000118 H -4.987176 1.540575 0.000141 H 2.473630 1.082656 -0.000097 H 6.082875 -0.203718 -0.881206 H 6.081956 -0.205245 0.883064 H 5.632227 -1.697053 -0.000537 Y C 2.180509 -2.924319 0.361203 C 2.422292 -1.554006 0.260304 C 1.351974 -0.690926 -0.009611 N 0.101007 -1.176171 -0.170580 C -0.135912 -2.488911 -0.074813 C 0.881397 -3.405980 0.191736 C 1.483543 0.784264 -0.139955 C 2.704780 1.454267 -0.003111 C 2.757119 2.839805 -0.137555 C 1.577929 3.533735 -0.408346 C 0.392384 2.814684 -0.534092 N 0.336312 1.474595 -0.404977 Pd -1.387337 0.365530 -0.581211 O -2.921075 -0.935196 -0.705581 C -4.175624 -0.624099 -0.949435 O -4.630647 0.499182 -1.142398 C -5.075404 -1.861509 -0.973537 H 3.429374 -1.174466 0.391043 H 3.611559 0.899110 0.207351 H 1.565779 4.612904 -0.521995 H 3.702172 3.364630 -0.032313 H 0.656210 -4.465345 0.263279 H 3.000553 -3.605645 0.570078 H -0.551369 3.302122 -0.743793 H -1.173053 -2.780545 -0.219713 H -2.347502 1.537032 -0.864418 H -5.024869 -2.383274 -0.010609 H -6.107954 -1.570166 -1.177988 H -4.732219 -2.562300 -1.743691
H 2.422899 4.239510 0.002488 H 4.432714 2.738733 0.001115 H 0.892719 -4.726585 -0.002352 H 3.285154 -3.982697 -0.002522 H 0.147661 3.225726 0.002479 H -0.935240 -2.967679 -0.000832 H 4.935281 -2.051690 -0.001801 H 5.345579 0.382242 -0.000482 H -1.858401 1.835746 0.002268 H -5.390692 -0.911826 -0.881601 H -5.387170 -2.468841 0.001450 H -5.390902 -0.910201 0.881781 O -2.848209 -2.493222 0.000140 Y_RETS N -0.761068 1.300388 0.053187 C -2.004319 0.750556 -0.010095 C -3.150304 1.553375 -0.096451 C -3.030934 2.940498 -0.101880 C -1.754298 3.498703 -0.020994 C -0.656123 2.646792 0.053053 C -2.094642 -0.735053 0.008325 C -3.253411 -1.407154 0.428709 C -3.268257 -2.801315 0.424316 C -2.127386 -3.489108 0.007068 C -1.012264 -2.742604 -0.378890 N -0.991455 -1.404539 -0.379346 Pd 0.931895 0.082447 -0.090930 O 2.816008 -0.943393 -0.186606 C 3.748885 -0.147254 0.113860 C 5.181437 -0.626598 0.124830 O 3.534598 1.081948 0.420948 H -4.119629 -0.856430 0.779807 H -4.128042 1.092268 -0.183840 H -1.601754 4.573499 -0.017956 H -3.913882 3.569167 -0.174527 H -2.094652 -4.574427 -0.013285 H -4.153507 -3.339670 0.752027 H 0.353297 3.035178 0.118079 H -0.093390 -3.228409 -0.699899 H 2.223092 1.102169 0.313427 H 5.241129 -1.676989 -0.168371 H 5.778981 -0.014813 -0.559366 H 5.601960 -0.497964 1.128134
S32
Y_HAATS C 1.377527 1.414390 -0.022814 C 1.412442 0.014232 -0.042480 N 2.573247 -0.651647 0.205050 C 3.693263 0.049308 0.470380 C 3.717845 1.440906 0.503268 C 2.536022 2.136354 0.251561 C 0.218882 -0.820325 -0.327671 C -1.044417 -0.279658 -0.596887 C -2.112135 -1.139524 -0.855987 C -1.892046 -2.514559 -0.840421 C -0.606153 -2.988705 -0.564432 N 0.417274 -2.158557 -0.314924 Pd 2.547522 -2.727161 0.159789 O 2.848275 -4.738893 0.196966 C 2.020054 -5.715230 -0.031889 C 2.668604 -7.088758 0.107186 O 5.453905 -3.122968 0.816530 O 6.130061 -2.062383 0.986061 H 4.183001 -2.863195 0.531040 H -0.352626 -4.046884 -0.535285 H -2.692846 -3.220498 -1.036929 H -3.098060 -0.734038 -1.066282 H 4.591425 -0.530131 0.660830 H 4.648281 1.954474 0.722261 H 2.512733 3.222199 0.267561 H -1.203907 0.792374 -0.606612 H 0.451418 1.940467 -0.220892 H 3.026502 -7.227382 1.133912 H 1.949384 -7.873055 -0.139599 H 3.540949 -7.161384 -0.551610 O 0.823844 -5.604832 -0.330218
Z C 2.123857 1.219088 0.888803 N 1.426379 -0.012590 0.417248 C 2.062509 -0.561768 -0.825425 C 3.602544 -0.686990 -0.737852 C 4.263963 0.619406 -0.280644 C 3.642615 1.076365 1.044498 C 1.279565 -1.004799 1.511158 C 0.646797 -2.333403 1.057487 C 1.495559 -2.917654 -0.078815 C 1.414778 -1.908802 -1.234647 C -0.828205 -2.290475 0.599848 N -1.028956 -1.448853 -0.633093 C -0.051644 -1.831178 -1.702013 C -2.413811 -1.699742 -1.153826 C -3.506669 -1.380543 -0.132645 C -3.273448 -2.105296 1.200246 C -1.832635 -1.887401 1.686466 H -0.170618 -1.114511 -2.519812 H -0.328054 -2.828223 -2.087299 H 2.528094 -3.081190 0.248205 H 1.104153 -3.893656 -0.394945 H 1.842948 0.179359 -1.606328 H 2.255230 -1.247259 1.963333 H 0.676754 -0.529516 2.291622 H 1.982518 -2.279134 -2.098981 H 0.671333 -3.004403 1.926999 H -1.069071 -3.329281 0.304018 H -2.537343 -1.092472 -2.053990 H -2.474470 -2.763390 -1.444814 H 1.898071 2.011106 0.169578 H 1.647572 1.520263 1.826629 H -1.636340 -2.489001 2.584313 H -1.684266 -0.833365 1.952440 H -3.535530 -0.298467 0.030207 H -4.472533 -1.672116 -0.565409 H -3.452993 -3.184211 1.077387 H -3.987450 -1.750405 1.953121 H 3.976653 -0.981805 -1.727697 H 3.888986 -1.489175 -0.045640 H 5.348043 0.480412 -0.182031 H 4.111358 1.398376 -1.042296 H 4.050761 2.047264 1.353774 H 3.897000 0.362858 1.841387 Pd -0.691829 0.648286 -0.261817 H -2.071409 1.072763 -0.775627 O -0.328395 2.629210 0.006244 C -1.246456 3.563759 -0.048207 C -0.658226 4.959922 0.174804 O -2.450823 3.410491 -0.247466 H -1.448222 5.712766 0.128034 H -0.161105 5.009555 1.150745 H 0.099278 5.175241 -0.588068
S33
Z_RETS
C 0.511898 2.531148 1.647728 C -0.485548 2.361475 0.495348 N 0.173305 1.639560 -0.645430 C 1.296759 2.488653 -1.145719 C 2.346588 2.775242 -0.070342 C 1.716572 3.371783 1.196693 C -0.789239 1.434292 -1.771260 C -2.167226 0.874705 -1.366227 C -2.784270 1.818456 -0.324279 C -1.857757 1.768663 0.896936 C -2.172172 -0.581595 -0.845484 N -1.518678 -0.683015 0.479821 C -1.887312 0.337869 1.467989 C -3.595613 -1.192916 -0.878766 C -3.607789 -2.628944 -0.332320 C -2.969224 -2.672540 1.063372 C -1.560383 -2.057669 1.010872 Pd 0.974957 -0.352414 -0.097349 O 1.931728 -2.247983 0.291246 C 3.127835 -2.205851 -0.084358 O 3.640097 -1.142921 -0.622367 C 4.035958 -3.398922 0.074361 H -0.298418 0.783912 -2.500893 H -0.969905 2.410343 -2.259924 H -3.801932 1.513963 -0.054722 H -2.850337 2.839632 -0.723594 H -1.547331 -1.184999 -1.522381 H -2.902730 0.181765 1.882093 H -1.189660 0.239205 2.308261 H -2.769783 0.884054 -2.285347 H -2.243933 2.429830 1.685256 H -0.721818 3.379011 0.123628 H 1.747793 1.969616 -1.996103 H 0.873584 3.442451 -1.515589 H -0.921987 -2.677340 0.367403 H -1.090444 -2.049175 2.000653 H 0.002056 3.015406 2.491936 H 0.852434 1.541882 1.979725 H 2.857823 1.838072 0.177079 H 3.095415 3.460872 -0.489364 H 1.382978 4.401501 0.997313 H 2.463210 3.432581 1.998405 H -3.964283 -1.176200 -1.914130 H -4.291378 -0.581780 -0.287941 H -4.633893 -3.018396 -0.307641 H -3.038234 -3.283040 -1.010214 H -2.899239 -3.706225 1.428115 H -3.601652 -2.127571 1.779308 H 2.683251 -0.401058 -0.596011 H 3.497156 -4.232448 0.528984 H 4.427322 -3.698440 -0.903847 H 4.894486 -3.128054 0.698565
Z_HAATS Pd 0.458780 0.698982 -0.231000 N 1.350213 -1.102549 0.554053 C 0.598381 -1.369835 1.823222 C -0.830460 -1.910266 1.617737 C -0.736554 -3.201391 0.790346 C -0.172125 -2.794949 -0.577153 C 1.268657 -2.276685 -0.384523 C 2.020874 -1.965965 -1.684171 C 3.504393 -1.688652 -1.400513 C 3.648933 -0.587335 -0.342103 C 2.791739 -0.870402 0.893251 N -1.471326 -0.633730 -0.451744 C -1.838418 -0.922275 0.976933 C -3.294055 -1.420129 1.150723 C -4.310599 -0.500879 0.459758 C -3.931669 -0.321223 -1.015409 C -2.499000 0.219768 -1.113398 H 1.714961 1.721626 0.253225 O 2.558873 2.690045 0.599138 O 3.374759 2.322619 1.502943 O -0.246506 2.494272 -0.929467 C -0.997910 3.173108 -0.109273 C -1.282938 4.598967 -0.564602 H -2.185838 0.362285 -2.152587 H -2.460299 1.192620 -0.621651 H -4.603266 0.394847 -1.506373 H -4.041700 -1.273114 -1.554422 H -4.314520 0.481024 0.953111 H -5.321776 -0.915507 0.559617 H -3.502631 -1.478469 2.227449 H -3.411556 -2.437947 0.756122 H -1.761232 0.047220 1.484689 H -2.082029 -2.416725 -1.466527 H 0.591756 -0.438719 2.398013 H -0.784461 -1.490895 -2.223058 H 1.158130 -2.120257 2.407356 H -1.209558 -2.133670 2.623939 H -0.075078 -3.925867 1.283895 H -1.712096 -3.686742 0.681101 H -0.089046 -3.677046 -1.226595 H 1.809177 -3.102740 0.114484 H 3.166978 -1.771188 1.409358 H 2.842127 -0.033981 1.594761 H 1.565836 -1.095117 -2.174105 H 1.912875 -2.820899 -2.364803 H 3.982532 -2.613350 -1.044122 H 4.023338 -1.400951 -2.322835 H 4.692776 -0.489796 -0.019160 H 3.357516 0.378180 -0.770030 H -1.412568 4.647693 -1.650247 H -0.423745 5.230562 -0.306331 H -2.167215 4.990450 -0.055320 C -1.167121 -1.838611 -1.257714 O -1.455655 2.735286 0.957664
S34
References
(1) Trend, R. M.; Stoltz, B. M. J. Am. Chem. Soc. 2004, 126, 4482-4483.
(2) Frisch, M. J. et al; Gaussian, Inc: Wallingford, CT, 2004.
(3) (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter 1988, 37, 785. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377.
(4) (a) The Stuttgart RSC 1997 ECP basis set for Pd was obtained from the Extensible Computational Chemistry Environment Basis Set Database, Version 02/25/04, as developed and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory which is part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, Washington 99352, USA, and funded by the U.S. Department of Energy. The Pacific Northwest Laboratory is a multi-program laboratory operated by Battelle Memorial Institute for the U.S. Department of Energy under contract DE-AC06-76RLO 1830. Contact Karen Schuchardt for further information. (b) Andrae, D.; Häußermann, U.; Dolg, M.; Stoll, H.; Preuß, H. Theor. Chim. Acta 1990, 77, 123-141.
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