# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
Electronic Supplementary Information
C-Cl / Si-H Exchange Catalysed by P,N-chelated Pt(II) Complexes
Frank Stöhr, Dietmar Sturmayr and Ulrich Schubert
Quantum chemical calculations
Quantum chemical calculations were carried out with the program package Gaussian98.1 The
system was simplified by replacing the chelating ligand Ph2PCH2CH2NMe2 by NH3 and PH3
groups and the hydridosilane HSiMe2Ph by SiH4.
Geometry optimizations of the equilibrium geometries were performed using the B3LYP
version of DFT. For the calculations the 6-31G++(d) basis set was used on all atoms, except
platinum where the relativistic effective core potential and basis set SDD was used. All these
basis sets are part of the Gaussian98 software package. Vibrational mode analyses were
carried out to confirm that on potential energy surfaces optimized geometries correspond to a
local minimum that has no imaginary frequency. Corrections of zero-point vibrational
energies were taken into account in stationary structures obtained.
A) Total energy difference between products and reactants
The calculations refer to the catalytic cycle given in Scheme 1
P
CH3
Pt
N
Cl
1
+ Cl-CDCl2
- Cl-CH3
H-SiMe2Ph
P
Cl
Pt
N
CDCl2
2
H-CDCl2
H
P
Pt
N
Cl
SiMe2Ph
CDCl2
Cl-CDCl2
P
H
Pt
N
CDCl2
1
Cl-SiMe2Ph 3
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E.Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J.
A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C.
Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford,
J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.
Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M.
Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon,
E. S. Replogle, J. A. Pople, Gaussian, Inc.: Pittsburgh, PA, 1998.
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
Activation Step
Pt
H3N
Cl
PH3
CH3
+ Cl-CH3-xClx
H3N
ClxH3-xC
PH3
Cl + Cl-CH3
Pt
Relative Energy [kcal/mol]
Cl-CH3
+9.0
Cl-CH2Cl
Cl-CHCl2
Cl-CCl3
+0.5
-4.7
-1.6
Step 1
H3N
ClxH3-xC
PH3
Cl
Pt
+ H-SiH3
H3N
ClxH3-xC
Pt
PH3
+ Cl-SiH3
H
Pt
PH3
Cl + H-CHyCl3-y
Relative Energy [kcal/mol]
H3N
H3C
Pt
PH3
Cl
-9.4
H3N
ClH2C
Pt
PH3
Cl
-9.5
H3N
Cl2HC
Pt
PH3
Cl
-10.1
H3N
Cl3C
Pt
PH3
Cl
-14.6
Step 2
H3N
ClxH3-xC
Pt
PH3
H
+ Cl-CHyCl3-y
H3N
ClxH3-xC
Relative Energy [kcal/mol]
Cl-CH3
Cl-CH2Cl
Cl-CHCl2
Cl-CCl3
H3N
H3C
Pt
PH3
H
-2.5
-7.6
-10.0
-14.4
H3N
ClH2C
Pt
PH3
H
-2.3
-7.4
-9.8
-14.2
H3N
Cl2HC
Pt
PH3
H
-1.8
-6.9
-9.3
-13.7
H3N
Cl3C
Pt
PH3
H
+2.7
-2.3
-4.8
-9.2
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
B) Total energy of possible intermediates
Cl and PH3 cis
Cl and PH3 trans
Energy [au] *
Energy [au] *
H3N
H3C
Pt
PH3
Cl
-1019.174956
H3N
Cl
Pt
PH3
CH3
-1019.189358
H3N
ClH2C
Pt
PH3
Cl
-1478.786038
H3N
Cl
Pt
PH3
CH2Cl
-1478.794463
H3N
Cl2HC
Pt
PH3
Cl
-1938.387684
H3N
Cl
Pt
PH3
CHCl2
-1938.395475
H3N
Cl3C
Pt
PH3
Cl
-2397.969058
H3N
Cl
Pt
PH3
CCl3
-2397.977224
* 1au = 27.21 eV = 627.51 kcal/mol
* 1au = 27.21 eV = 627.51 kcal/mol
H and PH3 cis
Energy [au] *
H3N
H3C
Pt
PH3
H
-559.536653
H3N
ClH2C
Pt
PH3
H
-1019.148006
H3N
Cl2HC
Pt
PH3
H
-1478.750477
H3N
Cl3C
Pt
PH3
H
-1938.339075
* 1au = 27.21 eV = 627.51 kcal/mol
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
C) Atomic coordinates of the calculated complexes after geometry optimization
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002
# Supplementary Material (ESI) for Chemical Comunications
# This journal is © The Royal Society of Chemistry 2002