Specific Molecular Orbital Contributions to Nucleophilicity. The Thiocarbonyl Group as Priviledged Monitor to Pinpoint Active and Less Active Molecular Orbitals in …

…, A Allouche, KF Purcell, M Chanon

Index: Arbelot, M.; Allouche, A.; Purcell, K. F.; Chanon, M. Journal of Organic Chemistry, 1995 , vol. 60, # 8 p. 2330 - 2343

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Citation Number: 8

Abstract

The rate constants for 41 compounds bearing a CS function reacting with MeX (X= I, Tos) span 7 orders of magnitude. The PES spectra of these compounds display two very low energy peaks, which stand clearly apart from the other peaks. These two peaks correspond to the n orbitals of the CS group; one is its CS n bonding orbital oriented out of the molecular plane (ncs) and the other its p-type in-plane lone pair orbital (ns). For some of the ...