Kinetics of ortho-carborane formation revisited

A kinetic study of ortho-carborane formation focusing on the reaction of various decaborane adducts [B 10H 12L 2; L=Me 2S, Ph 2S, tert-Bu 2S, (C 6F 5) 2S, MeSPh, MeSC 6F 5, MeS(sec-Bu)] with three acetylenes (propargyl bromide, 2-butyne-1,4-diacetate, 1-nonyne) has been carried out. For a given acet...

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Bibliographic Details
Published in:Inorganica Chimica Acta 1997-07, Vol.260 (1), p.99-103
Main Authors: Islam, S., Johnson, F.A, Hill, W.E., Silva-Trivino, L.M.
Format: Article
Language:English
Subjects:
Kinetics
Ortho-carborane
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Summary:A kinetic study of ortho-carborane formation focusing on the reaction of various decaborane adducts [B 10H 12L 2; L=Me 2S, Ph 2S, tert-Bu 2S, (C 6F 5) 2S, MeSPh, MeSC 6F 5, MeS(sec-Bu)] with three acetylenes (propargyl bromide, 2-butyne-1,4-diacetate, 1-nonyne) has been carried out. For a given acetylene, the rate constants decrease with both an increase in the electronegativity and/or an increase in size of substituents on sulfur. Yields of orthocarborane have been shown to increase as the size and/or basicity of the Lewis base increases and, for a given adduct, with the lower basicity of the acetylene.
ISSN:0020-1693
1873-3255
DOI:10.1016/S0020-1693(96)05544-2