Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2000
On the Electronic Character of Oxygen-Transfer Reactions
Dirk V. Deubel,* Gernot Frenking,* Hans Martin Senn, and Jörg Sundermeyer
S
S
electrophilic
attack
O
nucleophilic
attack
O
O
endo-SSO
S
S
S
O
endo-exo-SOSO
(+endo-endo-SOSO)
S
O
SSO2
Scheme Sup-1. Thianthrene 5-oxide (SSO) as a probe for the electronic character of
oxygen-transfer reactions.
Figure Sup-1. Optimized geometries (B3LYP/II) of the transition states for ethylene
epoxidation with dimethyldioxirane (DMDO), m-chloroperbenzoic acid (MCPBA),
and methyloxodiperoxorhenium(VII) [ReO(O2)2(CH3)].
Figure Sup-2. Predominant orbital interactions of donation d and backdonation b
according to the CDA of the transition states for ethylene epoxidation with DMDO
and MCPBA.
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Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2000
Standard density functional (DFT) methods for oxidations:
(1)
For geometry optimizations, Becke’s three-parameter hybrid functional (B3)3
together with the correlation functional of Lee, Yang, and Parr (LYP)4 were
employed as implemented in Gaussian 98.5 Our standard basis set II6 was used,
which consists of relativistic small-core ECPs7 and valence basis set splittings
(441/2111/21) for Re and (441/2111/31) for Mo, while the 6-31G(d)8 allelectron basis set was employed for the other atoms. All stationary points were
characterized by the calculation of vibrational frequencies. The zero-point
energy (ZPE) corrections are unscaled. Improved total energies were calculated
at the B3LYP level using the same ECP and valence basis set at Re and Mo, but
totally uncontracted and augmented with one set of f-type polarization functions
( = 0.869 for Re and  = 1.043 for Mo),9 together with the 6-31+G(d) basis set
at the other atoms.10 This basis-set combination is denoted III+.2
(2)
Deubel, D. V.; Frenking, G. J. Am. Chem. Soc. 1999, 121, 2021.
(3)
Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(4)
Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
(5)
Gaussian 98 (Revision A.3): Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.;
Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E.; Burant, J. C.; Dapprich. S.; Milliam, J. M.; Daniels,
A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski,
J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.;
Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomberts,
R.; Martin, R. L.; Fox, D. J.; Keith, T. A.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.;
Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.;
Pople, J. A. Gaussian Inc., Pittsburgh, PA, 1998
(6)
Frenking, G.; Antes, I.; Böhme, M.; Dapprich, S.; Ehlers, A. W.; Jonas, V.;
Neuhaus, A.; Otto, M.; Stegmann, R.; Veldkamp, A.; Vyboishchikov, S. F. in
Reviews in Computational Chemistry; Lipkowitz, K. B.; Boyd, D. B. Eds.;
VCH: New York, 1996, Vol. 8, p. 63.
(7)
Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
(8)
(a) Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939.
(b) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
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Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2000
(9)
Ehlers, A. W.; Böhme, M.; Dapprich, S.; Gobbi, A.; Höllwarth, A.; Jonas, V.;
Köhler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett.
1993, 208, 111.
(10)
Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput.
Chem. 1983, 4, 294.
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