Supporting Info - Shannon S. Stahl - University of Wisconsin–Madison

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

  S1

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, 1,3,5trimethoxybenzene (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 precooled (–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.

  S2

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   2

0.6 (Sp)Pd(H)Cl fit

0.2 0

Concentration (mM)

Concentration (mM)

0.8

0.4

O = 2.8 atm 2

0.7 0.6 0.5 0.4

(Sp)Pd(H)Cl fit

0.3 0.2 0.1 0

0

1000

2000 3000 Time (s)

4000

5000

0

1000

O = 4.3 atm 2

0.7

Concentration (mM)

O = 1 atm

1

2000 3000 Time (s)

4000

5000

0.6 0.5 0.4 (Sp)Pd(H)Cl fit

0.3 0.2 0.1 0 0

1000

2000 3000 Time (s)

4000

5000

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.

  S3

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 (IEFPCM).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). 1

1

S2

2

1

1

E spin "corrected "DFT = EUDFT +

3

S " S

[E 1

2

UDFT

" 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 ! The high-energy triplet species, predicted after the crossing point is subjected to method. 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-

  S4

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 multiconfigurational 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.

  S5

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-N2Pd-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–O 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 transitionstate optimization. No calculations proved fruitful as the potential energy surface is likely moreor-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. α

  S6

Triplet State (S=1) NACl

NA

NB Pd H

Free Energy {Total Energy} (kcal/mol)

30

Pd

+ O2 22.8

10

10.7 {11.8} NA

0

–10

0.0 {0.0} NA Pd H

Cl + O2

NB H Pd Cl + O2

NB 1

NA Cl Pd

NB H

NB O O

O O

18.6 {21.7}

20

Singlet State (S=0)

H

O O MECP

2TS

Cl

NB

3

21.4

MECP {1.4}

8.8 {11.1} NA Cl Pd O

H

O

O O 5 4 NA NB

Cl NA

8TS 13.8 {–0.4} 10.4 {–5.3}

NB H

Pd

Pd

6TS

12.8 {0.3} NA Cl

NB

15.0 {0.9}

H

B H N

O O

Pd 7

Cl NA NA

=

NB Pd

NA NB

Cl

–12.0 OOH {–27.9}

9

–20

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.

  S7

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).   S8

Figure S5. Energy profile for the reaction of zwitterionic complex 3 with O2 to form superoxide adduct 4.

  S9

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 Nchelating 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 πaccepting 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   sp phen bpy py-ox (lower E isomer) py-ox (higher E isomer)

N–Pd–N (degree) 84.77 78.72 77.85 76.70 77.54

Pd–Ntrans (Å) 2.33 2.20 2.18 2.24 2.21

Pd–Ncis (Å) 2.18 2.08 2.07 2.07 2.09

Pd–H (Å) 1.53 1.54 1.54 1.54 1.54

Pd–X (Å) 2.33 2.31 2.31 2.31 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 pyridineoxazoline 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-NN)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.

S10  

(A)

!G {!E} (kcal/mol)

40

O

O N H

N

N

30

H Pd 20

14.8

10

0

Pd DTS

Cl

BTS

Cl

N

14.0 {16.6}

{17.5}

16.3 {16.2}

14.7 {17.3}

O

O 0.0 {0.0}

-10

H Pd

O

Cl

N

N

N H

N

N

N Pd

Cl

E

C

Pd Cl

H

A

(B)

N !G {!E} (kcal/mol)

O

O

40

30

Pd

N

N H

Cl

Pd

N H

Cl

GTS

20 10

18.9

17.9

{21.6}

{21.0}

16.7 {20.0}

ITS 17.7 {18.3}

O 0

1.8 {2.1}

-10

Pd

N

N

N

N

O

O N

H

Cl

Pd H

N H

Cl J

Pd H

Cl F

Figure S6. Reaction pathways for reductive elimination from (py-ox)Pd(H)Cl complexes

S11  

40 N H

!G {!E} (kcal/mol)

30

N

N

20

Pd Cl

LTS

21.4 {24.7}

19.2 {23.3}

10

0

N H

0.0 {0.0}

-10

NTS

19.1 {21.9}

18.2 {20.0}

N

N H

Pd

Cl

N

N

H

Pd Cl

N

Pd Cl O

M

N Pd

Cl

H

K

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.

40

N N

!G {!E} (kcal/mol)

30

N

N

Pd Cl H

20

Pd Cl

QTS

20.2 {22.6}

10

17.7 {20.8}

{22.5}

19.2 {22.0}

UTS 19.1 {20.6}

N N

N

0.0 {0.0}

H

Pd Cl T

Pd

-10

N

Pd Cl

STS

19.7 15.5 {17.5} N

0

N H

H

Cl

H

N H

N

Pd Cl

R N

N Pd

Cl

H

P

Figure S8. Reaction pathways for reductive elimination from (bpy)Pd(H)Cl complex

S12  

V

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.

S13  

Solvation-Corrected Energies and Thermochemical Corrections at 298K (kcal/mol) and Three Lowest Frequencies from Normal-Mode Analysis

Total E

ZPE

H

S

Frequencies (cm-1)

Esol

s2

Gsol

Sg state

-94358.87

2.33

-94354.45

48.98

1633.4

-94356.90

2.009

-94368.98

Pd(NA-N B)(H)(Cl) - H cis to N A

-806694.92

259.46

-806424.00

130.62

51.0, 92.8, 99.2

-806817.23

0.000

-806587.15

TS HAA by O2

-901010.97

259.85

-900737.55

151.66

-1578.1, 25.1, 47.9

-901160.32

2.024

-900934.01

TS κ -κ 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

Label

Description

3

3

O2

1 1_HAA 2

TS

TS

–

2

1

MECP

1

-

+

Pd(η -O2)Cl --SpH (OSS)

-901169.67

0.949

-900939.98

Pd(η1-O2)Cl---SpH+ (SC-singlet)

-901163.05

Spin-corr

-900933.36

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

-901174.45

0.000

-900943.34

-901165.86

2.012

-900934.75

-50.2, 24.6, 38.5

-901173.21

0.000

-900941.16

1

-

+

Pd(η -O2)Cl --SpH (CCS)

5

-901027.26

265.31

-900748.16

154.63

19.4, 36.6, 49.4

Pd(η1-O2)Cl---SpH+ (OST) 6

TS

+

2

-901024.86

264.89

-900746.79

148.03

7

Pd(O2)(Cl)(κ1-NA -NBH) with N 2H 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(O 2)(Cl)(N A-N BH) by NBH

-901023.74

263.15

-900747.81

140.59

-904.4, 51.0, 83.7

-901174.49

0.000

-900942.36

-901050.64

265.42

-900772.08

143.46

42.1, 49.1, 76.4

-901201.99

0.000

-900968.09

9

TS for SpH reassociation to Pd(η -O2)Cl

-

2

Pd(Sp)(OOH)(Cl) - OOH cis to N (CSS)

NA-NB = Sp = (–)-sparteine

S14  

Label

Description py

ox

ox

Total E

ZPE

H

S

Frequencies (cm-1)

Esol

s2

Gsol

-679705.50

102.31

-679594.86

113.77

51.4, 63.1, 89.6

-679801.81

0.000

-679803.71

A

Pd(N -N )(H)(Cl) w/ H cis to N

A_HAATS

TS for HAA from Pd(N py-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

TS for κ2-κ1 isomerization Pd(κ -N ox-Npy)(H)(Cl)

-679687.86

100.86

-679578.52

118.25

-111.4, 18.1, 51.7

-679784.35

0.000

-679786.24

-679688.03

101.09

-679578.08

120.22

23.5, 51.3, 60.2

-679785.18

0.000

-679787.07

B

TS

1

1

py

Pd(κ -N -N )(H)(Cl) w/ H cis to N

C D

ox

TS

py

-679684.42

99.96

-679576.17

114.58

-735.3, 47.4, 63.2

-679784.48

0.000

-679786.37

E

Pd(κ1-Nox-N pyH)(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(N py-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

TS for κ - κ isomerization Pd(κ -N -N )(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-N ox)(H)(Cl) w/ H cis to N ox

-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-N py-Nox)(H)(Cl)

-679681.40

99.83

-679573.21

116.65

-538.8, 28.8, 49.8

-679781.80

0.000

-679710.28

Pd(κ -N -N H)(Cl)

-679682.86

102.45

-679571.91

116.93

35.0, 59.5, 70.1

-679783.52

0.000

-679709.32

(phen)Pd(H)(Cl)

-728173.67

114.74

-728050.32

113.65

54.7, 89.6, 97.9

-728275.30

0.000

-728187.73

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

TS for κ - κ isomerization

-728148.18

112.80

-728026.43

119.49

-265.9, 22.9, 56.1

-728250.58

0.000

-728166.35

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

TS for deprotonation of Pd(η -phen)(H)(Cl)

-728148.25

112.58

-728027.08

115.78

-95.5, 27.6, 75.8

-728253.36

0.000

-728168.61

Pd(κ1-phenH)(Cl)

-728149.50

114.22

-728026.44

117.82

31.4, 57.0, 76.0

-728255.62

0.000

-728169.58

(bpy)Pd(H)(Cl)

-680336.28

106.61

-680221.40

112.19

52.5, 75.2, 93.2

-680429.64

0.000

-680350.11

-774652.26

106.94

-774534.94

132.76

-1587.1, 26.4, 56.6

-774772.81

2.021

-774696.96

-680316.55

105.05

-680203.06

115.55

-65.0, 31.4, 48.6

-680407.07

0.000

-680329.92

R

TS for HAA from (bpy)Pd(H)(Cl) TS for κ2- κ1 isomerization Pd(κ1-bpy)(H)(Cl) w/ H cis to associated N 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

Pd(κ -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

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

Pd(κ1-bpyH)(Cl)

-680311.59

106.09

-680197.02

116.17

38.3, 47.4, 64.8

-680409.05

0.000

-680331.01

G

TS for deprotonation of Pd-H by N

py

2

TS

1

J K K_HAA L

TS

2

TS

M N

TS

P

QTS

V

py

ox

ox

1

TS

1

T U

1

1

O

P_HAA

py

1

TS

Npy-Nox = 2-(4,5-dihydro-2-oxazolyl)-pyridine phen = 1,10-phenanthroline bpy = 2,2’-bipyridine

S15  

Label

Description py

ox

Total E

ZPE

H

S

Frequencies (cm-1)

Esol

s2

Gsol

W W_RETS W_HAA TS

Pd(N -N )(H)(OAc) H cis to ox TS for R.E. from Pd( N py-Nox )(H)(OAc) TS for HAA from Pd( Npy-N ox )(H)(OAc)

-534288.32 -534279.14 -628607.79

133.56 131.66 134.17

-534144.01 -534136.76 -628460.78

136.10 137.75 157.44

26.9, 31.4, 40.7 -814.7, 25.1, 26.9 -1494.2,22.2,24.53

-534403.24 -534392.45 -628748.32

0.000 0.000 2.025

-534301.40 -534293.04 -628650.13

X X_RETS X_HAATS

Pd(phen)(H)(OAc) TS for R.E. from Pd(phen)(H)(OAc) TS for HAA from Pd(phen)(H)(OAc)

-582756.56 -582744.58 -677075.59

145.99 143.95 146.61

-582599.57 -582589.60 -676915.93

134.96 136.07 154.23

26.5, 37.0, 47.8 -828.3, 23.0, 38.6 -1470.8, 24.5, 28.2

-582876.79 -582863.20 -677221.77

0.000 0.000 2.023

-582761.93 -582750.68 -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

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

Pd(Sp)(H)(OAc)

-661279.11

290.89

-660974.39

154.03

11.8, 22.1, 43.5

-661419.01

0.000

-661162.10

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

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

Y_HAA

TS

Z Z_RE

TS

Z_HAATS

Npy-Nox = 2-(4,5-dihydro-2-oxazolyl)-pyridine phen = 1,10-phenanthroline bpy = 2,2’-bipyridine

S16  

Cartesian Coordinates for Optimized Complexes O2 O O

0.0000000 0.0000000

0.0000000 0.0000000

0.6028760 -0.6028760 2TS

1 C C N C C C C C C C C N C C C C C Pd Cl H H H H H H H H H H H H H H H H H H H H H H H H H H H

4.381832 2.876019 2.050294 2.345906 3.856482 4.640836 2.175696 1.451438 1.979565 1.608893 -0.090888 -0.598109 0.072764 -2.068629 -2.868261 -2.301760 -0.785575 -0.176937 0.095238 -0.248654 -0.296175 3.060395 1.516752 1.940907 3.232852 1.787093 1.935309 1.697876 -0.399130 -2.418088 -2.201697 2.504517 2.650759 -0.365524 -0.576567 -2.857580 -3.911624 -2.503626 -2.802280 3.957556 4.296719 5.711068 4.319823 4.873944 4.811703 -1.647772

1.272288 1.464447 1.386364 0.132480 -0.149792 -0.077583 2.632026 2.577259 1.375994 0.128077 2.505109 1.242386 0.037883 1.134097 2.332163 3.663114 3.728468 1.170235 1.037547 -0.826553 -0.102643 1.454025 1.333690 -0.680113 2.863171 3.446164 -0.778162 3.510892 2.454195 0.207618 1.042340 0.694178 2.421279 4.633498 3.773952 2.322088 2.208071 3.765258 4.503727 -1.144657 0.562031 -0.228205 -0.888245 1.319608 2.084339 0.950354

-3.286962 -3.499609 -2.258120 -1.486400 -1.293511 -2.609259 -1.458874 -0.101699 0.692498 -0.123240 -0.131606 -0.774803 -0.191964 -0.503499 -1.019078 -0.505201 -0.741858 -2.907328 -5.213255 -0.780429 0.839253 0.849852 1.687420 -2.104900 -1.251720 -2.078917 0.404687 0.422187 0.930189 -0.966148 0.588916 -4.180452 -3.978907 -0.282795 -1.818043 -2.113728 -0.700861 0.571805 -1.000709 -0.838683 -0.583683 -2.418764 -3.279714 -4.266852 -2.682768 -3.284019

C C C C H H C H H C H C H H H H N N H C H H C H H C H H C H H C H H C H H C H H C H H Pd Cl H

0.114180 1.587665 0.861600 -0.622501 -0.010871 -0.145396 1.685216 2.725178 1.289088 2.258933 1.990369 1.518536 2.464712 0.899566 2.130039 0.894632 1.718830 -0.891374 -0.851606 -2.247429 -2.417266 -2.257112 2.341994 2.056655 1.902358 -1.616684 -1.396366 -1.483186 -3.337876 -3.422685 -4.307997 -3.062661 -3.225768 -3.773981 3.805675 4.146489 4.139828 4.449373 5.540472 4.245666 3.876902 4.273165 4.186688 -1.326830 -2.004120 0.041820

-1.367790 -1.483755 -2.021645 -1.968902 -0.577644 -2.326143 -2.549663 -2.724434 -3.510890 -0.171215 0.617194 -0.728966 -1.033165 -0.269241 -1.817303 -2.743365 0.273713 -1.115084 -3.007559 -1.487941 -0.936749 -2.565875 1.514418 2.319816 1.770356 -1.610405 -2.221521 -0.559064 -1.171844 -0.079635 -1.484883 -1.856482 -2.938862 -1.503887 -0.271158 -0.505864 -1.095917 1.037436 0.928588 1.836699 1.446009 2.421889 0.719792 1.031936 3.193529 1.569613

-1.721200 -1.276303 1.004701 0.576531 -2.466676 -2.203803 -0.176412 0.121422 -0.532111 -0.811565 -1.534600 1.521825 2.014608 2.302676 -2.171733 1.832806 0.480918 -0.637118 0.268082 -1.154225 -2.084265 -1.394265 0.953252 0.260415 1.923900 1.687403 2.572528 1.975454 -0.123286 0.019619 -0.529629 1.224019 1.115983 1.980199 -0.823296 -1.841689 -0.179162 -0.335231 -0.286134 -1.064290 1.030870 1.341639 1.796530 -0.257139 0.045488 -0.551506

S17  

3 C C C C H H C H H C H C H H H H N N H C H H C H H C H H C H H C H H C H H C H H C H H Pd Cl H

4 0.073954 1.550442 0.827465 -0.659236 -0.073995 -0.143452 1.684305 2.727177 1.321698 2.192557 1.862471 1.452101 2.413837 0.815012 2.113170 0.869382 1.660505 -0.925686 -0.860536 -2.282837 -2.448819 -2.288332 2.319656 1.968434 1.901112 -1.661242 -1.431808 -1.553542 -3.382251 -3.451902 -4.341717 -3.098130 -3.236227 -3.816615 3.731607 4.045088 4.095112 4.372290 5.464302 4.135332 3.843957 4.238484 4.186037 -1.043285 -0.876281 0.546693

-1.431465 -1.476924 -2.014049 -1.995084 -0.682261 -2.423929 -2.522451 -2.662996 -3.497247 -0.134718 0.652733 -0.711984 -0.954246 -0.243663 -1.800492 -2.726835 0.324481 -1.152723 -3.044689 -1.507652 -0.927428 -2.580252 1.572409 2.378694 1.774625 -1.638910 -2.230361 -0.575821 -1.224874 -0.140324 -1.563061 -1.919650 -3.006034 -1.585878 -0.191624 -0.414914 -1.019410 1.118472 1.017929 1.926509 1.487683 2.458888 0.748828 1.058451 3.353224 0.711276

-1.719635 -1.265679 1.014369 0.571187 -2.501510 -2.157622 -0.150221 0.157424 -0.499802 -0.833145 -1.524923 1.549389 2.019309 2.306632 -2.151780 1.849155 0.499982 -0.644694 0.276856 -1.161652 -2.074311 -1.435810 1.001706 0.346745 1.991521 1.675014 2.572322 1.926722 -0.134533 0.016102 -0.547928 1.205907 1.096089 1.964293 -0.853945 -1.882024 -0.230349 -0.374545 -0.360750 -1.081058 1.017188 1.340300 1.756519 -0.321457 -0.028186 0.229420

Cl Pd O O N C C C C C C C N C C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H

-0.714594 -2.030479 -2.887392 -1.883912 1.358389 1.220788 2.545649 3.601718 3.768499 2.443783 2.562294 1.296408 0.128522 0.372590 1.613131 1.457710 2.841080 -0.879232 -2.099976 -2.317809 -1.053414 -1.187693 -0.858598 -2.592150 -3.141352 -1.939442 -2.986390 -0.661744 -1.112569 0.628329 1.513662 1.041985 3.392032 0.475527 2.985746 3.756213 1.766121 0.553852 2.320786 0.455781 0.821473 2.907273 2.355730 4.562434 3.290190 4.461831 4.221056 2.042772

-1.517741 -1.345725 -1.125363 -0.882562 -0.459124 -1.921950 -2.549007 -2.380827 -0.895035 -0.235181 1.273483 1.833056 1.819015 2.541580 1.931833 0.448329 2.087290 2.547866 3.106104 2.313048 2.305426 1.648664 3.330351 1.275419 2.736951 4.169338 3.052035 3.144383 1.530073 3.601535 2.864752 1.236393 1.379905 -0.184257 3.143105 1.757416 2.478183 0.259669 0.124503 -1.967869 -2.408163 -2.116797 -3.610020 -2.801014 -2.936996 -0.772862 -0.370748 -0.750942

2.189838 0.198196 -1.595499 -2.389932 -0.395768 -0.774257 -1.196320 -0.097321 0.249662 0.658158 0.965459 1.640158 0.747877 -0.515492 -1.217321 -1.601300 -0.308423 -1.407844 -0.666050 0.626565 1.482354 2.347705 1.860974 0.386415 1.214969 -0.429473 -1.309403 -2.304527 -1.742551 -0.294289 1.985072 2.523069 1.676537 0.087911 -0.048069 -0.815167 -2.157584 -2.184504 -2.189131 -1.552842 0.120213 -2.139610 -1.397110 -0.417466 0.797458 1.090993 -0.601741 1.538398

S18  

MECP Pd N C C C C C C C C C N C C C C C Cl O O H H H H H H H H H H H H H H H H H C H H H H H H H H H H

-1.788892 -0.296054 -1.650965 -2.653444 -2.138228 -0.744513 0.227092 1.651512 2.576782 2.030578 2.112801 1.358546 1.720738 3.544554 3.584084 2.857853 1.427530 -0.450927 -1.461081 -2.751450 0.854641 0.889295 2.801208 3.096739 4.623383 3.413253 3.990823 4.156731 2.733526 1.544740 1.031127 2.631245 3.616795 2.562701 2.004915 0.641823 0.165815 0.595994 0.335827 -0.327812 -0.837858 -1.977815 -1.603040 -2.084714 -2.824649 -3.611646 -2.825888 0.362193

5 -1.677368 1.699251 1.972695 2.319557 3.479090 3.131140 2.797834 2.443142 2.247778 1.046856 -0.255019 -0.071695 1.190435 -0.750626 -2.022850 -1.785599 -1.314480 -2.657385 -0.623589 -0.704465 -2.073128 -1.083896 -2.710934 -2.845307 -2.322685 -1.064075 -0.940319 0.028090 1.067204 -1.043674 1.247295 0.875918 2.097259 3.144470 3.279691 2.207794 0.505608 1.367664 3.715531 3.966057 2.270554 1.078468 2.805843 4.400370 3.679540 2.577465 1.438311 0.058876

0.016965 0.841206 1.357895 0.256506 -0.602407 -1.138980 0.004761 -0.491121 0.719646 1.507679 0.683657 -0.639308 -1.383610 0.437282 -0.420151 -1.749880 -1.507042 1.698449 -1.841837 -1.503656 -0.966859 -2.427794 -2.335492 0.119705 -0.598662 -2.365679 1.420965 -0.036351 -1.774334 1.191947 -2.228614 2.410172 0.405808 1.351502 -1.108759 2.687087 2.486143 1.964579 0.623614 -1.719199 -1.813174 1.899158 2.089546 -0.002215 -1.434061 0.725630 -0.371130 -0.365190

Pd N C C C C C C C C C N C C C C C Cl O O H H H H H H H H H H H H H H H H H C H H H H H H H H H H

0.144786 -0.173834 1.300125 1.852358 1.315999 -0.216329 -0.723338 -2.269813 -2.682195 -2.151926 -2.816917 -2.612016 -2.951230 -4.302498 -4.945164 -4.757669 -3.279610 -0.588479 -0.664310 0.639169 -2.724398 -3.099548 -5.134227 -4.478682 -6.010619 -5.338036 -4.361683 -4.866132 -4.037240 -2.278432 -2.645867 -2.390705 -3.769192 -2.233821 -2.635972 -0.207752 -0.217253 -0.619035 -0.382158 -0.632084 -0.574814 1.608356 1.717184 1.698557 1.656886 2.948644 1.569830 -1.584839

0.735171 -0.061459 -0.079209 -1.357771 -2.595530 -2.544100 -1.245421 -1.154545 0.117155 1.309314 1.387836 0.065013 -1.160236 1.772968 1.801661 0.447484 0.076796 2.914515 -1.098606 -1.204480 0.814043 -0.903497 0.480403 2.590300 2.046504 -0.330128 2.763366 1.090165 -1.193209 2.114688 -2.014685 2.253271 0.162600 0.121090 -2.045693 1.318754 2.021418 1.204464 -1.248108 -3.396405 -2.610950 0.795653 0.040561 -2.626657 -3.512802 -1.323746 -1.395654 -0.001089

-1.171247 2.497085 2.425371 1.794173 2.521126 2.540240 3.187893 3.236651 3.993052 3.181643 1.791166 1.042083 1.856125 1.837059 0.444181 -0.250747 -0.320503 -0.693931 -1.053833 -1.452811 -0.905868 -0.765111 -1.279973 -0.160734 0.527601 0.265320 2.304496 2.486072 1.975818 1.172089 1.248621 3.688327 4.132721 4.994306 3.763890 4.122411 2.488990 3.098584 4.246755 3.095476 1.505458 1.842466 3.447092 3.553148 2.025844 1.841398 0.735342 0.879671

S19  

6TS Pd N C C C C C C C C C N C C C C C Cl O O H H H H H H H H H H H H H H H H H C H H H H H H H H H H

7 -1.079367 -0.944661 -2.312069 -3.379895 -3.283300 -1.848322 -0.840370 0.620961 1.506174 1.469488 2.130693 1.474291 1.239122 3.654908 4.295377 3.637331 2.131432 -0.430745 -0.766278 -1.309656 1.899874 1.600661 4.027524 4.170287 5.372919 3.871173 4.064230 3.917001 2.202288 1.895146 0.596242 2.053478 2.525802 1.108094 0.615193 -0.272705 -0.048538 0.017321 -1.103680 -1.752423 -1.617285 -2.328726 -2.521552 -3.573307 -3.982818 -4.367586 -3.255742 0.512150

-1.566066 1.340929 1.343780 1.005404 1.938418 1.951283 2.298863 2.422922 2.906998 1.806775 0.508573 0.063433 1.150463 0.622763 -0.648853 -1.013323 -1.170467 -1.981595 -2.629328 -1.413724 -1.977907 -1.391899 -1.962563 -1.479814 -0.498478 -0.253556 0.840918 1.476849 1.393921 -0.309018 0.698752 2.112522 3.120194 3.842361 3.166015 2.558254 0.803022 1.627071 3.311267 2.694205 0.969128 0.620149 2.343678 2.959003 1.623682 1.078628 -0.037479 -0.278054

0.020204 0.707563 1.276600 0.235644 -0.978779 -1.524890 -0.418739 -0.918951 0.236988 1.308456 0.796723 -0.507355 -1.525708 0.643266 0.069338 -1.267379 -1.095921 2.250351 -1.651074 -1.986803 -0.396014 -2.024488 -1.651764 0.777379 -0.058854 -2.025916 1.637197 0.006987 -1.982650 1.489333 -2.286735 2.186059 -0.104029 0.650469 -1.727487 2.314852 2.508067 1.789989 -0.042969 -2.329117 -1.951467 2.097499 1.709306 -0.682348 -1.762154 0.707062 -0.088281 -0.230483

C C N C C C C C C C C N C C C C C Pd Cl H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

3.601792 2.088846 1.509502 2.184969 3.715017 4.275267 1.251013 0.721830 1.683389 1.601826 -0.726872 -0.923065 0.158490 -2.229311 -3.410528 -3.211673 -1.832882 -1.227858 -1.025870 0.046740 -0.013895 2.702770 1.377462 1.904715 2.191729 0.543140 2.228784 0.728936 -0.848790 -2.335695 -2.176350 1.806461 1.546996 -1.652425 -1.803465 -3.536287 -4.322769 -3.293253 -4.003682 4.135628 4.030618 5.361292 4.097062 3.945652 3.874746 0.533283 -1.239079 -1.258308

1.653187 1.713132 0.406035 -0.121914 -0.132552 1.219133 -0.583534 -1.938886 -2.478550 -1.502370 -2.006823 -1.209949 -1.504088 -1.609376 -1.357320 -2.039669 -1.697483 1.069355 1.518536 -0.785347 -2.515448 -2.568493 -3.482087 0.610543 -0.744457 -0.081823 -1.858168 -2.597067 -3.069584 -1.038951 -2.683301 2.457518 1.962960 -2.295401 -0.640874 -0.276133 -1.725369 -3.130761 -1.738272 -0.403044 -0.915106 1.146523 1.980668 2.648135 0.966067 0.688537 1.567125 2.705506

1.107903 0.934567 0.443363 -0.813469 -0.666476 -0.200302 1.549835 1.046561 -0.019995 -1.202446 0.492502 -0.765937 -1.757369 -1.381327 -0.442005 0.919417 1.509062 -0.437682 -2.781394 -2.573015 -2.164406 0.373521 -0.339479 -1.581193 2.086076 2.214388 -2.030726 1.925746 0.204533 -2.307716 -1.638306 0.183344 1.849094 2.413247 1.797144 -0.304067 -0.929020 0.798619 1.615092 -1.642781 0.035537 -0.069462 -0.972267 1.414545 1.921260 0.105271 1.529357 0.724834

S20  

8TS C C N C C C C C C C C N C C C C C Pd O O Cl H H H H H H H H H H H H H H H H H H H H H H H H H H H

9 1.858294 1.650758 0.491052 0.902570 1.167119 2.191816 0.146370 0.112695 1.504933 1.680302 -0.999001 -0.702395 0.733718 -1.242854 -2.143269 -1.590206 -1.533986 -1.431946 -1.354764 -2.692066 -2.508450 -0.802662 0.914252 1.609157 2.269518 -1.925634 1.091281 0.764261 -0.082106 2.688185 2.536563 0.093868 1.809302 -2.544597 -1.144226 2.682259 0.958388 0.215353 1.518394 3.194408 2.237780 -1.674626 -0.279935 -2.200222 -3.167422 -2.228514 -0.595157 -1.112307

-5.054533 -3.846842 -4.116790 -5.241539 -6.520907 -6.304627 -2.914124 -1.588010 -1.361335 -2.452606 -1.351329 -1.975524 -2.118233 0.178611 0.645163 0.115922 -1.405411 -4.725732 -4.329764 -4.611712 -5.184967 -3.121318 -2.787220 -0.366249 -1.440002 -1.839627 -1.183104 -2.888674 -0.828854 -2.396725 -3.797772 -5.395505 -4.931208 -1.806113 -1.843860 -4.836731 -5.225067 -6.873743 -7.296336 -6.181209 -7.189707 0.474583 0.701906 1.740454 0.272720 0.403707 0.541105 -3.162810

0.251721 -0.669778 -1.603806 -2.506048 -1.708249 -0.582864 -2.417629 -1.632873 -1.032222 0.024961 -0.557963 0.802874 1.190025 -0.486241 0.659688 1.983507 1.923308 -0.693375 1.294567 0.901889 -2.743748 -2.916410 -3.200962 -0.583124 -1.814930 -0.881935 1.641926 1.968348 -2.401360 0.459143 -1.330170 -3.223173 -3.054629 1.783586 2.846911 0.945231 0.854450 -1.292142 -2.400985 -1.019444 0.063115 -1.450267 -0.405673 0.663085 0.515549 2.828086 2.178825 0.960913

C N C C C C C C C C C N C C C C C Pd Cl O O H H H H H H H H H H H H H H H H H H H H H H H H H H H

-2.425923 -1.442660 -1.904638 -3.394950 -4.332640 -3.878092 -1.190342 -0.317856 -0.973516 -1.002516 1.146857 1.269162 0.453400 2.710701 3.658603 3.467014 1.980243 0.431916 2.171031 -0.356220 -0.810845 0.499480 0.925105 -1.975781 -0.389530 -1.793220 -2.144113 -0.733939 -1.446312 -0.279105 1.597543 2.792808 2.969673 -2.358443 -2.062155 1.817692 1.638646 3.495887 4.685855 3.828373 4.059148 -3.646274 -3.551359 -5.367090 -4.306563 -4.488652 -4.011080 0.040686

0.747767 -0.169833 -0.529918 -0.943765 0.055617 0.261111 -1.363755 -2.437533 -2.872794 -1.625136 -2.049825 -0.936328 -1.214528 -0.837326 -0.601210 -1.632070 -1.737766 0.960828 2.375586 2.606032 3.454002 -0.320607 -2.040128 -3.277668 -3.670726 0.397308 -1.836790 -0.998395 -1.870335 -3.284307 -2.941702 -0.018834 -1.781328 1.710277 0.914983 -2.535353 -0.796652 0.409709 -0.632635 -2.619957 -1.352660 -1.042137 -1.933440 -0.307197 1.018707 1.024117 -0.667338 3.819665

-1.136522 -0.465296 0.932093 1.015133 0.329889 -1.117594 -1.322978 -0.655843 0.660341 1.557158 -0.374336 0.628682 1.849862 1.037722 -0.139956 -1.258658 -1.623521 -0.113014 0.679042 -0.867076 0.206150 2.479620 2.409772 0.485916 1.136981 1.507431 -1.597684 -2.247426 2.531173 -1.354448 0.099888 1.754900 1.547873 -0.630434 -2.153647 -2.360944 -2.073895 -0.523526 0.245528 -0.934053 -2.138503 2.079590 0.568239 0.375376 0.859145 -1.616698 -1.690893 0.522608

S21  

1_HAATS C C N C C C C C C C C N C C C C C Pd Cl H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

1.441640 0.635227 0.996999 2.451703 3.351552 2.947939 0.208072 -1.308066 -1.532068 -0.889004 -2.049533 -1.631967 -1.624896 -3.581540 -4.354209 -3.954288 -2.435928 0.569292 0.321248 0.428606 0.571119 -2.596148 -1.063184 -1.738813 -2.652317 -1.170621 -1.728555 -1.023852 0.956443 2.700852 2.600464 -2.144823 -2.109897 1.131788 1.210430 3.301199 4.388372 3.189376 3.521204 -3.790344 -3.938530 -5.434207 -4.122896 -4.436770 -4.296641 2.018717 3.092844 3.576721

-1.926737 -2.174354 -1.157872 -1.311241 -1.117836 -2.042601 -1.369774 -1.529324 -2.708383 -2.303400 -0.267219 0.082647 -1.068865 -0.419370 0.785057 1.029110 1.218530 0.882206 3.089380 -0.530684 -2.289209 -2.932374 -3.618051 0.590858 -1.384820 -0.719559 -1.761341 -3.103796 -3.154339 -0.588340 -2.323806 2.111980 1.386770 -2.661485 -0.929351 -0.073272 -1.305486 -3.085440 -1.797500 -0.553325 -1.327345 0.613889 1.680470 1.933123 0.194448 1.546325 2.159774 1.570995

-1.820101 -0.538856 0.510778 0.832895 -0.389576 -1.545216 1.763476 1.543998 0.584660 -0.747603 1.035585 -0.363081 -1.297644 1.205901 0.653126 -0.806139 -0.903322 -0.134622 -0.834898 2.430519 2.254856 0.454416 0.982290 1.646797 -1.541396 -2.230160 2.531669 -1.487760 -0.138176 1.613663 1.247936 -0.345100 -1.933358 -2.575202 -2.215987 -0.716493 -0.083526 -1.290099 -2.447305 2.275899 0.703525 0.744815 1.248451 -1.198969 -1.434475 0.447024 0.938971 1.952847

S22  

A_HAATS

A Pd N N C C C C C H H H H C O C C H H H Cl H H

0.142298 0.277828 2.353089 3.342349 4.688418 5.004666 3.971192 2.658824 3.026951 5.465627 6.040639 4.168651 1.471652 1.598444 0.237572 -0.676093 0.135223 0.137467 -1.316020 0.195764 -1.391787 -1.314170

0.005031 0.003587 0.002313 0.001874 0.000055 -0.001379 -0.000954 0.000927 0.003007 -0.000230 -0.002828 -0.002057 0.001550 -0.000320 0.000847 0.003277 -0.892951 0.893655 -0.881623 0.006099 0.006881 0.889671

0.502432 2.565700 0.874088 -0.021936 0.363187 1.722217 2.663621 2.192052 -1.062601 -0.394671 2.048949 3.730308 3.054792 4.394595 4.937052 3.683104 5.556177 5.557976 3.615126 -1.805061 0.401893 3.617259

BTS C C N C O Pd Cl C N C C C C H H H H H H H H H

C N C O C Pd Cl C N C C C C H H H H H H H H H O O

-0.682294 0.272082 1.465077 1.593676 0.232697 0.135234 0.122479 2.659762 2.371007 3.370052 4.711779 5.011550 3.966791 3.071369 5.497579 6.043497 4.151663 0.132104 0.134221 -1.325331 -1.559797 -1.323656 -2.859283 -3.302554

0.003114 0.003123 0.001315 -0.000058 0.001194 0.005134 0.007205 0.000724 0.002240 0.001902 0.000016 -0.001552 -0.001199 0.003181 -0.000203 -0.003030 -0.002371 -0.892407 0.894230 -0.878828 0.007138 0.886382 0.008611 0.007967

3.667690 2.548001 3.036675 4.375062 4.919807 0.462510 -1.847147 2.181247 0.861056 -0.023932 0.376384 1.738976 2.667903 -1.069091 -0.372583 2.078024 3.736788 5.539385 5.540545 3.600149 0.403635 3.601632 0.430730 1.619196

-1.476921 0.030879 0.156313 -1.035931 -2.057145 2.088190 4.246215 -1.464201 -0.515706 -0.886677 -2.222314 -3.208522 -2.830306 1.539575 0.638225 0.404294 -1.924239 -1.734269 -3.566865 -4.257743 -2.472715 -0.082302

0.038586 -0.144485 -0.054178 -0.057067 -0.086246 0.007175 0.083724 -0.037966 -0.123094 -0.104133 -0.002746 0.081599 0.063876 -0.140904 0.630856 -1.121939 -0.729038 1.030906 0.128583 0.160838 0.008387 -0.173884

-0.232486 0.018974 1.492832 1.987777 1.092526 2.238278 2.956887 3.405812 4.350118 5.629808 6.038186 5.056317 3.713265 3.630092 -0.455913 -0.306204 -0.866238 -0.615396 2.921223 5.327022 7.094822 6.359000

C -1.499072 0.018592 0.145305 -1.040802 -2.062324 2.073005 4.226794 -1.452461 -0.491384 -0.842876 -2.164439 -3.162191 -2.807047 1.747116 0.449619 0.574794 -1.819934 -1.902840 -3.551522 -4.200974 -2.396042 -0.033257

-0.005760 0.085984 -0.018593 0.069726 0.165273 -0.240206 -0.503797 0.080689 0.248366 0.249553 0.087890 -0.076261 -0.078646 0.611911 1.040167 -0.720910 -0.983353 0.783149 -0.203260 -0.201856 0.094221 0.386906

-0.270803 -0.028733 1.444192 1.945361 1.057453 2.185705 2.866881 3.367704 4.287238 5.572895 6.008163 5.048243 3.698654 3.379211 -0.350853 -0.513662 -0.643827 -0.907471 2.920871 5.340769 7.069204 6.286633

C C N C O Pd Cl C N C C C C H H H H H H H H H

S23  

DTS C C N C C C C N C C O Pd Cl H H H H H H H H H

E -2.816695 -1.479432 -0.482341 -0.728483 -2.033934 -3.088019 -1.097910 0.109033 0.005573 -1.501406 -2.116281 1.867544 3.764917 0.747348 0.629853 0.380583 -1.944741 -1.740754 -3.611488 -4.117285 -2.216387 0.145966

0.007176 -0.025675 -0.038015 -0.017225 0.015540 0.027314 -0.048451 -0.072972 -0.138022 0.059303 -0.051364 -0.087796 -0.099745 -0.063330 0.639444 -1.111759 -0.707103 1.051844 0.016805 0.052796 0.031376 -0.027795

3.727274 3.306957 4.217039 5.527577 6.016164 5.094675 1.893399 1.426183 -0.048402 -0.324209 0.991082 2.462854 3.757120 3.688179 -0.494898 -0.380551 -0.962489 -0.717598 2.990415 5.440931 7.085728 6.173144

-2.117101 -1.104164 0.116571 0.010256 -1.486058 -1.484240 -2.818437 -3.080784 -2.020989 -0.723399 -0.489190 1.867603 3.764463 0.536625 0.665298 0.346292 -1.941218 -1.691160 -3.616328 -4.108692 -2.203350 0.159467

-0.078118 -0.059023 -0.078003 -0.164487 0.083732 -0.031621 -0.006209 0.017604 0.016841 -0.008531 -0.032997 -0.072231 -0.063774 -0.049688 0.577432 -1.159783 -0.636507 1.102217 -0.005324 0.037540 0.035776 -0.010447

0.976166 1.893538 1.433283 -0.043058 -0.323671 3.285619 3.731082 5.094153 6.022844 5.540292 4.218088 2.428813 3.723635 3.819540 -0.503862 -0.352994 -1.005686 -0.669754 2.997992 5.444270 7.091495 6.171824

0.000792 0.000094 0.000291 0.000655 -0.000603 -0.000116 -0.000285 0.000236 0.000056 -0.000007 0.000122 0.000311 0.000362 -0.000468 -0.000162 0.000070 0.000411 0.000498 -0.895064 0.891885 -0.882384 0.885569 -0.000772 -0.000644

3.366322 2.223368 2.675456 4.012447 4.595661 -0.011027 -0.501150 1.782053 0.456519 -0.430915 -0.038211 1.319838 2.249909 -1.700331 -1.479070 -0.797791 1.652491 3.318251 5.217000 5.219711 3.316612 3.316967 -2.995003 -3.335388

F_HAATS

F C C N C C C C N C C O Pd H H H H H H H H Cl H

O C N C C C C C C C N Pd Cl H H H H H H H H H

3.880150 2.546964 2.174211 3.142855 4.499937 4.877588 1.420669 0.206101 -0.669738 0.325277 1.650005 0.111825 0.217205 2.804911 5.239743 5.925781 4.115975 0.265164 0.267509 -1.315515 -2.170284 -1.313623

-0.001341 0.000751 0.002572 0.002318 0.000263 -0.001597 0.001222 0.003175 0.003047 0.000861 -0.000420 0.005531 0.006961 0.003807 0.000148 -0.003205 -0.002712 -0.892898 0.893892 -0.879920 0.008640 0.887438

2.608713 2.203236 0.892792 -0.038958 0.289091 1.631985 3.145587 2.737771 3.913796 5.106742 4.475280 0.528610 -1.005466 -1.068210 -0.505109 1.915763 3.667371 5.731603 5.732872 3.886444 0.221034 3.888099

C N C O C Pd Cl C N C C C C H H H H H H H H H O O

-0.921884 -0.002327 1.196047 1.374548 0.028164 -0.014743 -2.267201 2.362423 2.053145 3.061011 4.402426 4.716484 3.674584 0.177244 2.775403 5.177682 5.750278 3.861404 -0.053330 -0.053894 -1.566095 -1.563965 0.327823 1.551508

S24  

GTS

H

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

C C N C C C Pd Cl C N C C O H H H H H H H H H

ITS

J

O C N C C C C C C C N Pd Cl H H H H H H H H H

1.643402 1.383981 0.140680 -0.692416 0.358456 2.533945 3.828394 4.926353 4.689734 3.379867 2.294955 0.450245 -1.602715 3.165711 5.506707 5.936642 3.952444 0.301627 0.360441 -1.288974 -0.093080 -1.375636

-0.072504 0.009423 0.075856 -0.006186 0.001202 0.006314 -0.000739 -0.005704 -0.003787 0.002063 0.005912 0.006257 -0.009983 0.002416 -0.007147 -0.010238 -0.000674 -0.860781 0.924212 -0.924032 0.057546 0.846723

4.360364 3.039021 2.712878 3.917098 5.056200 2.122806 2.661874 1.809147 0.430888 -0.033701 0.778013 -0.163123 -1.183212 -1.096692 -0.283939 2.206355 3.738461 5.723205 5.641261 3.886187 1.380998 3.958685

N C C C C C C O C C N Pd Cl H H H H H H H H H

-1.159077 0.050973 0.150428 -1.002677 -2.257516 -2.342762 2.149002 4.339463 -0.961769 -0.038325 -0.458161 -1.893125 -2.084065 1.787158 0.992008 -1.160172 -3.310355 -3.147735 -2.669071 -2.020037 0.243818 -0.421111

-0.123585 -0.104470 -0.056528 -0.042566 -0.041977 -0.085826 0.127521 0.391538 -0.039200 -0.486853 -0.259720 0.316288 0.474226 -0.360323 -0.122463 -0.161929 -0.092483 -0.012017 -0.362643 1.299091 0.434330 -1.202601

-0.750094 -0.064138 1.282208 1.998801 1.374351 -0.014306 1.922117 2.473142 3.482451 4.236651 5.625699 5.508675 4.073794 3.298704 -0.605937 -1.834659 -0.507371 1.990865 5.874154 5.967990 6.102102 6.180500

2.282472 2.539901 3.844631 4.932380 4.681854 3.376000 1.414610 1.630279 0.338417 -0.706330 0.148602 0.465574 -1.621531 3.158826 5.495784 5.946054 3.973534 0.279827 0.334401 -1.227758 -0.125589 -1.448187

0.014374 0.005468 -0.013127 -0.022404 -0.011621 0.006910 0.006600 -0.088570 0.036048 -0.058288 0.081812 0.043655 0.053604 0.015132 -0.017450 -0.035882 -0.017697 -0.770121 1.004091 -1.021291 0.089507 0.743610

0.778445 2.130357 2.665011 1.810229 0.426702 -0.034798 3.040076 4.359608 5.037877 3.903267 2.724030 -0.158489 -1.115289 -1.096361 -0.291793 2.197970 3.741545 5.769851 5.545506 3.874275 1.664614 3.937425

S25  

K_HAATS

K C C C N C C C C C C N C C C Pd H H H H H H H H H Cl

2.545249 2.595610 1.381538 0.187173 0.172921 1.332645 1.385629 2.596568 3.810819 3.808956 0.198760 0.156134 1.310121 2.527971 -1.434090 1.256571 3.456171 1.228024 3.433452 -0.792463 -0.826569 4.736086 4.732654 -2.491783 -3.148888

-2.840523 -1.434927 -0.757472 -1.414932 -2.743414 -3.490536 0.675869 1.399702 0.684321 -0.673526 1.281850 2.600314 3.403044 2.803988 -0.180828 -4.568674 -3.394961 4.478144 3.399095 -3.221842 3.016898 1.246488 -1.206266 -1.301617 1.303763

0.414598 0.277449 0.002644 -0.130525 0.004712 0.277582 -0.145130 -0.015981 0.262737 0.403059 -0.407899 -0.551557 -0.440176 -0.172923 -0.531280 0.376471 0.625566 -0.565285 -0.081924 -0.108439 -0.760267 0.360453 0.613905 -0.593056 -0.972728

LTS C C C N C C C C C C N C C C Pd Cl H H H H H H H H H

C C C N C C C C C C N C C C Pd Cl H H H H H H H H H O O

2.538111 2.605653 1.394076 0.209808 0.166822 1.321507 3.819987 3.818084 2.604806 1.390257 0.198684 0.182761 1.344990 2.555736 -1.446591 -3.211755 1.268936 3.467995 1.240011 3.444276 -0.783551 -0.813638 4.745052 4.741688 -2.613652 -3.492753 -2.969640

2.807278 1.402709 0.679008 1.287863 2.606239 3.408236 0.687941 -0.669900 -1.430759 -0.754767 -1.415442 -2.742708 -3.488741 -2.837026 -0.177158 1.248256 -4.566813 -3.389429 4.483375 3.401305 -3.226817 3.027064 1.250383 -1.202780 -1.420741 -2.376274 -3.516139

-0.171598 -0.014767 -0.143815 -0.406256 -0.550024 -0.438669 0.263718 0.404030 0.278549 0.004028 -0.128185 0.006627 0.279599 0.415947 -0.533568 -0.978532 0.378470 0.626767 -0.563733 -0.080547 -0.105911 -0.758684 0.361223 0.614733 -0.601497 -0.650895 -0.443905

2.771659 2.712735 1.441889 0.342419 0.415484 1.624035 1.353761 2.561528 3.813272 3.890219 0.167340 0.168319 1.309237 2.515435 -1.797548 -3.962198 1.640515 3.731566 1.224898 3.432134 -0.521550 -0.794513 4.701390 4.840344 -1.256064

-2.883866 -1.481174 -0.890272 -1.666273 -2.976345 -3.644143 0.562005 1.318823 0.674757 -0.671886 1.193973 2.526876 3.330116 2.718801 0.465242 -0.195044 -4.722426 -3.349050 4.403468 3.295952 -3.522536 2.981918 1.296416 -1.155404 -0.915889

0.494682 0.325658 0.047538 -0.044529 0.116658 0.391361 -0.133880 -0.016689 0.265496 0.430016 -0.406976 -0.557043 -0.454648 -0.182631 -0.665941 -0.967852 0.516340 0.706288 -0.589734 -0.093615 0.024927 -0.771356 0.343739 0.642858 -0.395264

M 2.491225 2.547298 1.345849 0.155696 0.147390 1.282478 3.797372 3.874052 2.701483 1.435374 0.333144 0.408768 1.608055 2.755950 -1.848276 -4.050124 1.617667 3.709109 1.191462 3.402716 -0.521250 -0.816712 4.682984 4.822153 -1.429033

2.713048 1.313619 0.549332 1.171485 2.502781 3.315392 0.674359 -0.671685 -1.486144 -0.901202 -1.665257 -2.974505 -3.643502 -2.888056 0.468476 -0.056772 -4.721258 -3.354978 4.387654 3.297741 -3.527368 2.951118 1.298342 -1.150492 -0.924977

-0.191434 -0.024062 -0.151820 -0.423126 -0.577975 -0.471607 0.276516 0.451386 0.329850 0.021968 -0.109501 0.059229 0.377138 0.506725 -0.629874 -0.881044 0.509055 0.743922 -0.610731 -0.096795 -0.062827 -0.803347 0.364561 0.683700 -0.981537

C C C N C C C C C C N C C C Pd Cl H H H H H H H H H

S26  

NTS N H Pd Cl N C C C C C C C C C C C C H H H H H H H H

O 0.024503 0.128383 0.979607 -0.725492 2.540235 2.471479 1.192443 1.169645 2.394875 3.588605 3.659916 4.912212 4.957801 3.753488 -1.148869 -1.256011 -0.087634 -2.022758 -2.231294 -0.119473 2.349306 4.521864 5.821509 5.898050 3.759951

0.006913 0.008105 -0.008954 0.035327 -0.049522 -0.051477 -0.022816 -0.026078 -0.057297 -0.084028 -0.081905 -0.110026 -0.107442 -0.076883 0.033304 0.032097 0.002213 0.055920 0.054109 0.000061 -0.059113 -0.107768 -0.133276 -0.128397 -0.074176

0.036277 1.519285 2.829997 4.362331 1.437916 0.066335 -0.641246 -2.067871 -2.810248 -2.160198 -0.725431 -0.077436 1.302892 2.014147 -0.573776 -1.974871 -2.713878 0.073854 -2.450569 -3.800694 -3.896204 -2.716885 -0.672175 1.844435 3.099058

2.665003 2.662215 1.423607 0.311338 0.307246 1.491080 1.347859 2.567150 3.801584 3.855223 0.148092 0.167997 1.319533 2.533696 -1.711779 -3.739814 1.481880 3.605460 1.244829 3.450443 -0.660103 -0.790814 4.703913 4.794752 -0.654085

-2.865480 -1.464609 -0.817766 -1.593942 -2.917985 -3.601724 0.615250 1.352083 0.672789 -0.676760 1.236367 2.579024 3.360163 2.747946 0.365874 -0.696782 -4.679445 -3.365980 4.434599 3.324183 -3.400298 3.036777 1.273089 -1.177894 -1.045440

0.477654 0.317458 0.034493 -0.064894 0.085336 0.363286 -0.141731 -0.019849 0.266123 0.429112 -0.415219 -0.564951 -0.459578 -0.184713 -0.631044 -0.855958 0.484598 0.693575 -0.594715 -0.095614 -0.023130 -0.779044 0.350048 0.644946 -0.290789

-2.118776 -0.785737 -0.306984 -1.198419 -2.559535 -2.977465 0.103981 -0.515679 0.190656 1.579026 2.237874 1.496213 -2.698232 -3.254913 -4.381184 -0.392714 2.121190 3.317996 -4.026958 -3.294091 -0.832719 2.002160 0.754244 -5.657526 -5.944464

0.021549 -0.149605 -0.408160 -0.492165 -0.314913 -0.060070 -0.046141 0.207693 0.320693 0.183786 -0.078622 -0.195321 0.401774 0.817619 0.526046 0.525324 0.281455 -0.192018 0.085042 -0.370603 -0.692571 -0.399112 -0.543549 0.619180 0.448208

P_HAATS

P Pd N C C C C C C C C C C N H Cl H H H H H H H H

C C C N C C C C C C N C C C Pd Cl H H H H H H H H H

2.416392 2.590325 1.416414 1.361444 2.536110 3.738141 3.719574 0.231934 -1.059226 -2.125721 -1.879318 -0.575362 0.459812 2.158693 4.638824 4.612404 4.672481 2.508916 -0.328104 -2.676171 -3.129301 0.423938 -1.232409

-2.696357 -0.530039 0.090820 1.482734 2.225616 1.567402 0.179054 -0.800233 -0.323686 -1.215271 -2.576988 -2.991873 -2.133376 -4.214925 -3.180509 -0.406945 2.111025 3.305714 -4.035854 -3.311600 -0.851497 1.987316 0.737511

0.400687 0.210576 -0.043926 -0.194040 -0.077440 0.185643 0.323153 -0.146985 -0.405571 -0.489200 -0.311377 -0.057064 0.024811 0.511497 0.811349 0.528116 0.283223 -0.191421 0.088654 -0.366890 -0.689493 -0.398504 -0.541144

N C C C C C C N C C C C Pd Cl H H H H H H H H H O O

0.449416 0.225299 -1.064344 -2.132056 -1.887922 -0.583364 1.411337 2.584723 3.715643 3.735908 2.534191 1.358691 2.423139 4.629507 2.142815 4.609647 4.671048 2.507714 -0.343338 -2.684719 -3.134996 0.421866 -1.237448 1.923389 0.696692

S27  

QTS C N Pd H Cl N C C C C C C C C C H H H H H H H H

R -0.102534 -0.079329 1.558877 2.212079 3.300807 -0.599875 -0.495846 -0.865678 -1.365303 -1.476059 -1.080077 -1.174695 -2.321825 -2.344600 -1.212254 0.800479 -1.179742 -3.227219 -3.175614 -1.844501 -1.653908 -0.753780 -0.093941

0.242877 0.224566 0.781024 1.566675 1.363671 -1.361763 -1.420053 -0.372456 0.799039 0.877565 -0.228387 -0.208532 -0.632113 -0.611864 -0.166215 0.595239 -0.133776 -0.940060 -0.978698 1.776430 1.641166 -0.473994 -2.346860

-0.004342 1.344493 2.509230 1.391229 3.850399 4.049897 5.384204 6.232015 5.663249 4.273902 3.510153 2.011933 1.339970 -0.054718 -0.737609 -0.488415 -1.821951 -0.596390 1.913381 3.788513 6.285959 7.307324 5.787616

STS C N Pd H N C C C C C C C C C Cl H H H H H H H H

C C N C C C Pd Cl C N C C C C H H H H H H H H H

-1.209634 -0.115002 -0.141986 -1.286762 -2.416969 -2.381951 1.553272 3.366140 -1.298832 -2.062765 -2.060312 -1.300992 -0.535835 -0.547745 2.548147 0.821792 -1.132609 -3.253003 -3.296844 -2.690763 -1.321450 0.058252 -0.044715

0.169605 0.501880 0.434093 0.033324 -0.336405 -0.265459 0.811150 1.234054 -0.023328 -0.985086 -1.109926 -0.301593 0.716806 0.872942 0.678494 0.824914 0.244906 -0.542158 -0.674795 -1.900257 -0.465542 1.384078 1.735110

-0.735787 0.055164 1.402912 2.013849 1.275868 -0.113597 2.578872 3.902349 3.501287 4.048047 5.378749 6.232444 5.667903 4.280296 1.439020 -0.382198 -1.815707 -0.700836 1.810639 5.781441 7.305581 6.285175 3.830337

-0.857351 -0.009458 1.293384 2.282025 1.883125 0.525964 -0.389634 -1.861233 -2.728282 -4.104049 -4.599296 -3.692023 -2.350760 -1.261577 -0.186762 -4.030631 -5.663796 -4.778129 -2.293634 1.557542 3.328275 2.611780 0.189403

-1.359318 0.255832 0.252146 0.728050 1.247174 1.253282 0.728945 0.702789 0.917495 0.919951 0.699581 0.473063 0.471959 -0.033304 -0.551680 0.266016 0.688630 1.091644 1.076545 -0.150663 0.696378 1.641922 1.658672

0.266316 4.085477 4.381677 3.514746 2.283732 1.960402 2.883714 2.638096 3.721302 3.525615 2.238370 1.211824 1.393148 -0.340122 -2.270257 0.202159 2.027744 4.360171 4.700819 5.357577 3.804319 1.581333 1.012626

T -0.057013 -0.031989 1.958076 1.702187 -1.827296 -1.927168 -1.462356 -0.874885 -0.751855 -1.225112 -1.176100 -2.340733 -2.349716 -1.182975 4.151857 0.876723 -1.135234 -3.249870 -3.221181 -2.405048 -1.569652 -0.517961 -0.314922

0.414386 0.324363 0.317589 0.925525 -1.110411 -1.168179 -0.162534 0.967333 1.035114 -0.037988 -0.015027 -0.332706 -0.259234 0.139234 0.200105 0.708730 0.227896 -0.498528 -0.631219 -2.059404 -0.262134 1.783609 1.903993

0.031416 1.382002 2.105043 3.458894 4.058213 5.391291 6.243278 5.673194 4.285555 3.517219 2.026143 1.311584 -0.076839 -0.733284 2.669429 -0.440152 -1.813790 -0.635986 1.868998 5.793089 7.319370 6.295135 3.806115

H N C C C C C C C C C C N Pd Cl H H H H H H H H

S28  

UTS H N C C C C C C C C C C N Pd Cl H H H H H H H H

V -0.516653 0.652671 0.728058 1.881429 2.960555 2.857452 1.674591 1.502275 2.634978 2.514137 1.244578 0.159749 0.259075 -1.552014 -3.527351 -0.842129 1.086758 3.386125 3.603255 -0.167527 1.926090 3.869716 3.675017

-0.891153 -1.484117 -2.821448 -3.478100 -2.700932 -1.310978 -0.703572 0.775756 1.589739 2.974196 3.523065 2.666304 1.314696 0.291574 -0.883179 3.054622 4.596337 3.607469 1.134984 -3.345435 -4.562372 -3.174334 -0.705049

0.428568 0.458157 0.441806 0.027460 -0.406910 -0.399897 0.050287 0.069702 0.234041 0.206892 0.009999 -0.124819 -0.087212 -0.073803 0.000189 -0.266960 -0.026680 0.343288 0.412101 0.765457 0.030533 -0.767623 -0.773913

-2.406610 -1.893183 -2.727687 -4.095861 -4.614147 -3.748804 -0.432378 0.330259 1.667867 2.354496 1.613270 0.231764 -1.433626 -0.257077 -0.191869 -4.116531 -5.675339 -4.743368 -2.303914 2.141362 3.432827 2.117846 -0.327007

-0.000657 0.777591 1.568038 1.604155 0.838596 0.063017 0.808227 -0.211769 -0.261836 0.746354 1.827951 1.863038 -1.450468 -3.083223 -0.954565 -0.550618 0.831185 2.204119 2.128989 -1.130387 0.696726 2.652370 2.722279

1.467112 2.470909 3.285022 3.062894 2.010125 1.255401 2.697693 2.234894 2.352528 3.006406 3.507838 3.349674 0.360473 -0.759509 1.551604 0.441253 1.781938 3.694993 4.110309 1.903995 3.111351 4.003286 3.700081

-0.654468 -0.348833 -1.289465 -2.569336 -2.977730 -1.999399 1.039800 1.380169 2.851467 3.290983 2.036202 0.031173 -1.186098 -0.459805 -1.082408 0.832523 -3.297281 -4.035028 -2.276178 0.140781 3.847778 3.847684 3.187406 0.975717 3.187397 -2.171438 -0.749292 -0.749186

-0.000035 -0.000005 0.000036 0.000041 0.000012 -0.000026 -0.000010 -0.000004 0.000004 0.000038 -0.000019 -0.000004 -0.000005 -0.000001 -0.000005 0.000000 0.000071 0.000022 -0.000048 -0.000066 -0.892699 0.892841 -0.884756 -0.000010 0.884746 0.000057 -0.882047 0.881956

W_RETS

W C C N C C C C N C C O Pd O C C O H H H H H H H H H H H H

N C C C C C C N C C C C Pd Cl H H H H H H H H H

-2.927277 -1.904846 -0.593990 -0.254905 -1.215188 -2.567364 -2.125808 -1.142064 -1.694103 -3.227607 -3.373744 0.744009 2.460719 3.670703 4.751037 3.962937 0.813058 -0.900556 -3.334178 -3.965223 -3.739246 -3.723425 -1.346284 1.524088 -1.331323 4.636692 5.742392 4.647837

1.820589 0.872121 1.207095 2.497820 3.516447 3.171198 -0.579288 -1.414009 -2.775523 -2.542139 -1.083960 -0.606748 0.443191 -0.069683 1.013866 -1.262092 2.699526 4.555350 3.940379 1.505125 -2.906189 -2.928802 -3.298184 -1.928048 -3.323867 1.664551 0.555721 1.643850

-0.043180 -0.022537 -0.017244 -0.032314 -0.053434 -0.058896 -0.004386 0.014420 0.029355 0.012980 -0.006812 0.017616 0.016159 0.032487 0.026364 0.050950 -0.027041 -0.065243 -0.075161 -0.046696 0.906458 -0.879949 0.925305 0.041546 -0.845019 0.901308 0.038106 -0.864936

C C N C C C C N C C O Pd O C C O H H H H H H H H H H H H

-3.670301 -2.303876 -1.339584 -1.710655 -3.049337 -4.044047 -1.820147 -0.577911 -0.512417 -1.998284 -2.740362 0.974283 2.728079 3.754037 5.127051 3.680824 -0.901415 -3.298547 -5.094782 -4.408855 -2.293864 -2.293845 0.036170 2.479724 0.036204 5.050037 5.684562 5.684623

S29  

W_HAATS O C N C C C C C C C N Pd O C C O O H H H H H H H H H H H H O

3.873515 2.608725 2.405590 3.701279 4.704956 1.517181 1.714277 0.593225 -0.659045 -0.767305 0.302685 0.466920 -1.336894 -2.496673 -3.637240 1.263705 2.507775 -1.709432 -1.553650 0.702874 2.711586 5.440320 5.212774 3.895018 0.955917 3.670139 -3.457662 -4.587989 -3.680828 -2.711487

X -0.153580 0.006243 0.024300 -0.146467 -0.267937 0.152631 0.136064 0.285332 0.442499 0.447518 0.305026 0.269102 0.495519 0.647865 0.788959 0.148610 -0.012166 0.565165 0.561279 0.278103 0.010509 0.538504 -1.233469 0.714197 0.196267 -1.036174 1.652135 0.912597 -0.097059 0.682412

2.579546 2.154274 0.881621 0.204127 1.378989 3.122877 4.502738 5.325238 4.735996 3.337261 2.548083 0.199504 -0.706584 -0.137101 -1.139748 -2.687434 -2.866207 2.806898 5.339619 6.406090 4.910574 1.416814 1.428010 -0.441985 -1.399312 -0.430849 -1.790601 -0.616240 -1.783150 1.081807

X_RETS C C C N C C C C C C N C C C Pd O C C O H

-2.662161 -2.813507 -1.640566 -0.385863 -0.281779 -1.390048 -1.780132 -3.081115 -4.239362 -4.108537 -0.654763 -0.769422 -2.013426 -3.170024 1.298863 3.192211 4.129837 5.571360 3.921631 -1.228283

C C C N C C C C C C N C C C Pd O C C O H H H H H H H H H H H H

3.434236 3.146557 1.784219 0.759849 1.064570 2.391040 1.445679 2.469756 3.841651 4.164012 0.127337 -0.230761 0.717445 2.065243 -1.128078 -2.857407 -4.063715 -5.150995 -4.348677 2.573614 4.468007 0.379570 2.818206 0.224045 -1.301723 4.622423 5.204983 -1.900797 -5.041579 -6.139396 -5.051001

-2.275618 -0.891607 -0.503236 -1.414242 -2.714710 -3.182675 0.898164 1.877040 1.451314 0.124710 1.223440 2.500729 3.544815 3.232872 -0.585359 0.446158 -0.076419 1.000512 -1.270399 -4.252506 -2.611762 4.576398 4.017319 -3.398158 2.687362 2.207663 -0.188183 -1.916317 1.648234 0.535900 1.634787

0.000354 0.000267 0.000054 -0.000068 0.000023 0.000235 -0.000029 0.000105 0.000314 0.000392 -0.000229 -0.000300 -0.000180 0.000022 -0.000348 -0.000634 -0.000083 0.001237 0.000190 0.000303 0.000521 -0.000249 0.000116 -0.000068 -0.000459 0.000412 0.000552 -0.000418 -0.876471 -0.006993 0.889936

-3.260974 -1.876764 -0.980135 -1.403632 -2.708697 -3.672965 -1.352302 -0.006626 0.928581 0.439509 1.275440 2.594791 3.159118 2.329686 0.363256 -0.232453 -1.433898 -1.441999 2.920789 3.985555

-0.001893 -0.001153 -0.000349 -0.000273 -0.000972 -0.001802 -0.001182 -0.000452 0.000369 0.000424 0.001185 0.001892 0.001891 0.001134 0.001110 0.001185 0.000669 0.000632 0.003047 0.003478

X_HAATS 2.927044 1.523194 0.718870 1.268336 2.603715 3.466021 -0.726327 -1.303480 -0.456128 0.900091 -1.480264 -2.802514 -3.470582 -2.714310 0.029543 -0.994463 -0.138038 -0.605019 1.117492 4.539534

0.000095 0.000059 -0.000013 -0.000094 -0.000075 0.000035 -0.000021 0.000036 0.000085 0.000099 -0.000067 -0.000050 0.000021 0.000060 -0.000080 -0.000104 0.000029 0.000308 0.000004 0.000062

C C C N C C C C C C N C C C Pd O C C O O

2.471632 2.766427 1.668709 0.377328 0.121795 1.154166 4.102983 4.330621 3.240191 1.909287 0.826297 1.031901 2.320776 3.425479 -1.045236 -2.990251 -3.489084 -5.014546 -2.619649 -1.928279

S30  

H H H H H H H H H H H

-3.543865 -2.044917 -4.148990 0.729188 0.161041 -5.223913 -4.987176 2.473630 6.082875 6.081956 5.632227

3.563135 -4.556096 -3.188228 2.997616 -3.363023 -0.917802 1.540575 1.082656 -0.203718 -0.205245 -1.697053

0.000161 0.000051 0.000118 -0.000177 -0.000118 0.000118 0.000141 -0.000097 -0.881206 0.883064 -0.000537

2.422899 4.239510 0.002488 4.432714 2.738733 0.001115 0.892719 -4.726585 -0.002352 3.285154 -3.982697 -0.002522 0.147661 3.225726 0.002479 -0.935240 -2.967679 -0.000832 4.935281 -2.051690 -0.001801 5.345579 0.382242 -0.000482 -1.858401 1.835746 0.002268 -5.390692 -0.911826 -0.881601 -5.387170 -2.468841 0.001450 -5.390902 -0.910201 0.881781 -2.848209 -2.493222 0.000140

Y_RETS

Y C C C N C C C C C C C N Pd O C O C H H H H H H H H H H H H

H H H H H H H H H H H H O

2.180509 2.422292 1.351974 0.101007 -0.135912 0.881397 1.483543 2.704780 2.757119 1.577929 0.392384 0.336312 -1.387337 -2.921075 -4.175624 -4.630647 -5.075404 3.429374 3.611559 1.565779 3.702172 0.656210 3.000553 -0.551369 -1.173053 -2.347502 -5.024869 -6.107954 -4.732219

-2.924319 -1.554006 -0.690926 -1.176171 -2.488911 -3.405980 0.784264 1.454267 2.839805 3.533735 2.814684 1.474595 0.365530 -0.935196 -0.624099 0.499182 -1.861509 -1.174466 0.899110 4.612904 3.364630 -4.465345 -3.605645 3.302122 -2.780545 1.537032 -2.383274 -1.570166 -2.562300

0.361203 0.260304 -0.009611 -0.170580 -0.074813 0.191736 -0.139955 -0.003111 -0.137555 -0.408346 -0.534092 -0.404977 -0.581211 -0.705581 -0.949435 -1.142398 -0.973537 0.391043 0.207351 -0.521995 -0.032313 0.263279 0.570078 -0.743793 -0.219713 -0.864418 -0.010609 -1.177988 -1.743691

N C C C C C C C C C C N Pd O C C O H H H H H H H H H H H H

-0.761068 -2.004319 -3.150304 -3.030934 -1.754298 -0.656123 -2.094642 -3.253411 -3.268257 -2.127386 -1.012264 -0.991455 0.931895 2.816008 3.748885 5.181437 3.534598 -4.119629 -4.128042 -1.601754 -3.913882 -2.094652 -4.153507 0.353297 -0.093390 2.223092 5.241129 5.778981 5.601960

1.300388 0.750556 1.553375 2.940498 3.498703 2.646792 -0.735053 -1.407154 -2.801315 -3.489108 -2.742604 -1.404539 0.082447 -0.943393 -0.147254 -0.626598 1.081948 -0.856430 1.092268 4.573499 3.569167 -4.574427 -3.339670 3.035178 -3.228409 1.102169 -1.676989 -0.014813 -0.497964

0.053187 -0.010095 -0.096451 -0.101880 -0.020994 0.053053 0.008325 0.428709 0.424316 0.007068 -0.378890 -0.379346 -0.090930 -0.186606 0.113860 0.124830 0.420948 0.779807 -0.183840 -0.017956 -0.174527 -0.013285 0.752027 0.118079 -0.699899 0.313427 -0.168371 -0.559366 1.128134

S31  

Y_HAATS C C N C C C C C C C C N Pd O C C O O H H H H H H H H H H H H O

1.377527 1.412442 2.573247 3.693263 3.717845 2.536022 0.218882 -1.044417 -2.112135 -1.892046 -0.606153 0.417274 2.547522 2.848275 2.020054 2.668604 5.453905 6.130061 4.183001 -0.352626 -2.692846 -3.098060 4.591425 4.648281 2.512733 -1.203907 0.451418 3.026502 1.949384 3.540949 0.823844

Z 1.414390 0.014232 -0.651647 0.049308 1.440906 2.136354 -0.820325 -0.279658 -1.139524 -2.514559 -2.988705 -2.158557 -2.727161 -4.738893 -5.715230 -7.088758 -3.122968 -2.062383 -2.863195 -4.046884 -3.220498 -0.734038 -0.530131 1.954474 3.222199 0.792374 1.940467 -7.227382 -7.873055 -7.161384 -5.604832

-0.022814 -0.042480 0.205050 0.470380 0.503268 0.251561 -0.327671 -0.596887 -0.855987 -0.840421 -0.564432 -0.314924 0.159789 0.196966 -0.031889 0.107186 0.816530 0.986061 0.531040 -0.535285 -1.036929 -1.066282 0.660830 0.722261 0.267561 -0.606612 -0.220892 1.133912 -0.139599 -0.551610 -0.330218

C N C C C C C C C C C N C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H Pd H O C C O H H H

2.123857 1.426379 2.062509 3.602544 4.263963 3.642615 1.279565 0.646797 1.495559 1.414778 -0.828205 -1.028956 -0.051644 -2.413811 -3.506669 -3.273448 -1.832635 -0.170618 -0.328054 2.528094 1.104153 1.842948 2.255230 0.676754 1.982518 0.671333 -1.069071 -2.537343 -2.474470 1.898071 1.647572 -1.636340 -1.684266 -3.535530 -4.472533 -3.452993 -3.987450 3.976653 3.888986 5.348043 4.111358 4.050761 3.897000 -0.691829 -2.071409 -0.328395 -1.246456 -0.658226 -2.450823 -1.448222 -0.161105 0.099278

1.219088 -0.012590 -0.561768 -0.686990 0.619406 1.076365 -1.004799 -2.333403 -2.917654 -1.908802 -2.290475 -1.448853 -1.831178 -1.699742 -1.380543 -2.105296 -1.887401 -1.114511 -2.828223 -3.081190 -3.893656 0.179359 -1.247259 -0.529516 -2.279134 -3.004403 -3.329281 -1.092472 -2.763390 2.011106 1.520263 -2.489001 -0.833365 -0.298467 -1.672116 -3.184211 -1.750405 -0.981805 -1.489175 0.480412 1.398376 2.047264 0.362858 0.648286 1.072763 2.629210 3.563759 4.959922 3.410491 5.712766 5.009555 5.175241

0.888803 0.417248 -0.825425 -0.737852 -0.280644 1.044498 1.511158 1.057487 -0.078815 -1.234647 0.599848 -0.633093 -1.702013 -1.153826 -0.132645 1.200246 1.686466 -2.519812 -2.087299 0.248205 -0.394945 -1.606328 1.963333 2.291622 -2.098981 1.926999 0.304018 -2.053990 -1.444814 0.169578 1.826629 2.584313 1.952440 0.030207 -0.565409 1.077387 1.953121 -1.727697 -0.045640 -0.182031 -1.042296 1.353774 1.841387 -0.261817 -0.775627 0.006244 -0.048207 0.174804 -0.247466 0.128034 1.150745 -0.588068

S32  

Z_RETS C C N C C C C C C C C N C C C C C Pd O C O C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H

0.511898 -0.485548 0.173305 1.296759 2.346588 1.716572 -0.789239 -2.167226 -2.784270 -1.857757 -2.172172 -1.518678 -1.887312 -3.595613 -3.607789 -2.969224 -1.560383 0.974957 1.931728 3.127835 3.640097 4.035958 -0.298418 -0.969905 -3.801932 -2.850337 -1.547331 -2.902730 -1.189660 -2.769783 -2.243933 -0.721818 1.747793 0.873584 -0.921987 -1.090444 0.002056 0.852434 2.857823 3.095415 1.382978 2.463210 -3.964283 -4.291378 -4.633893 -3.038234 -2.899239 -3.601652 2.683251 3.497156 4.427322 4.894486

Z_HAATS 2.531148 2.361475 1.639560 2.488653 2.775242 3.371783 1.434292 0.874705 1.818456 1.768663 -0.581595 -0.683015 0.337869 -1.192916 -2.628944 -2.672540 -2.057669 -0.352414 -2.247983 -2.205851 -1.142921 -3.398922 0.783912 2.410343 1.513963 2.839632 -1.184999 0.181765 0.239205 0.884054 2.429830 3.379011 1.969616 3.442451 -2.677340 -2.049175 3.015406 1.541882 1.838072 3.460872 4.401501 3.432581 -1.176200 -0.581780 -3.018396 -3.283040 -3.706225 -2.127571 -0.401058 -4.232448 -3.698440 -3.128054

1.647728 0.495348 -0.645430 -1.145719 -0.070342 1.196693 -1.771260 -1.366227 -0.324279 0.896936 -0.845484 0.479821 1.467989 -0.878766 -0.332320 1.063372 1.010872 -0.097349 0.291246 -0.084358 -0.622367 0.074361 -2.500893 -2.259924 -0.054722 -0.723594 -1.522381 1.882093 2.308261 -2.285347 1.685256 0.123628 -1.996103 -1.515589 0.367403 2.000653 2.491936 1.979725 0.177079 -0.489364 0.997313 1.998405 -1.914130 -0.287941 -0.307641 -1.010214 1.428115 1.779308 -0.596011 0.528984 -0.903847 0.698565

Pd N C C C C C C C C C N C C C C C H O O O C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H C O

0.458780 1.350213 0.598381 -0.830460 -0.736554 -0.172125 1.268657 2.020874 3.504393 3.648933 2.791739 -1.471326 -1.838418 -3.294055 -4.310599 -3.931669 -2.499000 1.714961 2.558873 3.374759 -0.246506 -0.997910 -1.282938 -2.185838 -2.460299 -4.603266 -4.041700 -4.314520 -5.321776 -3.502631 -3.411556 -1.761232 -2.082029 0.591756 -0.784461 1.158130 -1.209558 -0.075078 -1.712096 -0.089046 1.809177 3.166978 2.842127 1.565836 1.912875 3.982532 4.023338 4.692776 3.357516 -1.412568 -0.423745 -2.167215 -1.167121 -1.455655

0.698982 -1.102549 -1.369835 -1.910266 -3.201391 -2.794949 -2.276685 -1.965965 -1.688652 -0.587335 -0.870402 -0.633730 -0.922275 -1.420129 -0.500879 -0.321223 0.219768 1.721626 2.690045 2.322619 2.494272 3.173108 4.598967 0.362285 1.192620 0.394847 -1.273114 0.481024 -0.915507 -1.478469 -2.437947 0.047220 -2.416725 -0.438719 -1.490895 -2.120257 -2.133670 -3.925867 -3.686742 -3.677046 -3.102740 -1.771188 -0.033981 -1.095117 -2.820899 -2.613350 -1.400951 -0.489796 0.378180 4.647693 5.230562 4.990450 -1.838611 2.735286

-0.231000 0.554053 1.823222 1.617737 0.790346 -0.577153 -0.384523 -1.684171 -1.400513 -0.342103 0.893251 -0.451744 0.976933 1.150723 0.459758 -1.015409 -1.113398 0.253225 0.599138 1.502943 -0.929467 -0.109273 -0.564602 -2.152587 -0.621651 -1.506373 -1.554422 0.953111 0.559617 2.227449 0.756122 1.484689 -1.466527 2.398013 -2.223058 2.407356 2.623939 1.283895 0.681101 -1.226595 0.114484 1.409358 1.594761 -2.174105 -2.364803 -1.044122 -2.322835 -0.019160 -0.770030 -1.650247 -0.306331 -0.055320 -1.257714 0.957664

S33  

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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. (5) (a) Cancès, E.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032-3041. (b) Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 106, 5151-5158. (c) Mennucci, B.; Cancès, E.; Tomasi, J. J. Phys. Chem. B 1997, 101, 10506-10517. (d) Tomasi, J.; Mennucci, B.; Cancès, E. J. Mol. Struct. THEOCHEM 1999, 464, 211-226. (6) (a) Cramer, C. J. Essentials of Computational Chemistry: Theories and Models, 1st ed.; Wiley: New York, 2002, page 341-342. (b) Kelly, C. P.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2006, 110, 16066-16081. (7)

Siegbahn, P. E. M. J. Bio. Inorg. Chem. 2006, 11, 695-701.

(8) (a) NBO 5.9. E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, and F. Weinhold (Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2004) http://www.chem.wisc.edu/~nbo5 (b) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735. (9) (a) Yamaguchi, K.; Jensen, F.; Dorigo, A.; Houk, K. N. Chem. Phys. Lett. 1988, 149, 537-542. (10) (a) Harvey, J. N.; Aschi, M.; Schwarz, H.; Koch, W. Theor. Chim. Acta 1998, 99, 95-99. (b) Harvey, J. N.; Aschi, M. Phys. Chem. Chem. Phys., 1999, 1, 5555-5563. (11) Schlegel, H. B. In: Modern electronic structure theory, Yarkony D. R. ed.; World Scientific: Singapore, 1995, p 459. (12) (a) Konnick, M. M.; Guzei, I. A.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 10212-10213. (b) Popp, B. V.; Stahl, S. S. J. Am. Chem. Soc. 2007, 129, 4410-4422. (c) Popp, B. V.; Stahl, S. S. Chem. Eur. J. 2009, 15, 2915-2922.

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S35