Are J(Si-H) NMR coupling constants really a probe for the existence of nonclassical H-Si interactions?

Journal of the American Chemical Society

Volumn 125, Issue 3, 2003, Pages 642-643

  Dubberley, Stuart R ^a   Ignatov, Stanislav K ^b   Rees, Nicholas H ^a   Razuvaev, Alexei G ^b   Mountford, Philip ^a   Nikonov, Georgii I ^c  

^a UNIVERSITY OF OXFORD   (United Kingdom)

^b LOBACHEVSKY STATE UNIVERSITY OF NIZHNY NOVGOROD   (Russian Federation)

^c MOSCOW STATE UNIVERSITY   (Russian Federation)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN; SILICON;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL INTERACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; CORRELATION ANALYSIS; ELECTRON TRANSPORT; MAGNETISM; NUCLEAR MAGNETIC RESONANCE; STRUCTURE ANALYSIS;

EID: 0037460135     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027935v     Document Type: Article

References (15)

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7. (a) Nikonov, G. I.; Kuzmina, L. G.; Vyboishchikov, S. F.; Lemenovskii, D. A.; Howard, J. A. K. Chem.-Eur. J. 1999, 5, 2497.
8. (b) Bakhmutov, V. I.; Howard, J. A. K.; Keen, D. A.; Kuzmina, L. G.; Leech, M. A.; Nikonov, G. I.; Vorontsov, E. V.; Wilson, C. C. Dalton Trans. 2000, 1631.
9. Nikonov, G. I.; Mountford, P.; Ignatov, S. K.; Green, J. C.; Cooke, P. A.; Leech, M. A.; Kuzmina, L. G.; Razuvaev, A. G.; Rees, N. H.; Blake, A. J.; Howard, J. A. K.; Lemenovskii, D. A. Dalton Trans. 2001, 2903.
10. w = 0.095.
11. Bent, H. A. Chem. Rev. 1961, 61, 275.
12. Basicity of the hydride is a prerequisite of IHI.
13. All calculations were carried out with the Gaussian 98 program package (Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, 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.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; 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 98, revision A.3; Gaussian, Inc.: Pittsburgh, PA, 1998) using density functional theory applying Becke's 1988 nonlocal exchange functional in conjunction with Perdew's correlation functional, commonly aliased as BP86. The compound basis set was used for the calculation consisted of the 6-31G basis set for the silicon, phosphorus and nitrogen atoms, 6-31G for the carbon atoms and the sylil hydrogens, and the 3-21G basis set for the hydrogen atoms of Cp ring and methyl groups. The basis set augmented by the p-polarization function (6-31G(d,p) basis set) was used for the hydride H atom. The Hay-Wadt VDZ effective core potentials (ECP) and the corresponding VDZ basis sets were used for the tantalum atom, and the "Stuttgart" quasi-relativistic ECP were used for the atom Cl in this model. For more details and references see ref 3.
14. Wiberg K. B. Tetrahedron 1968, 24, 1024.
15. F. R. Lemke has recently made a similar observation (private communication).