Building a Picture of Heteroborane Isomerisation: Synthesis and Characterisation of the 10-(Dialkyl- sulfane)-7,8-diphenyl-7,8-dicarba-nido-undecaboranes 7,8-Ph2-10-L-7,8-nido-C2B9H10 (L = SMe2, SMeEt, SEt2) and of Intermediate and Isomerised Products Arising from Metallation of the First of These
- 1 January 1999
- journal article
- Published by Institute of Organic Chemistry & Biochemistry in Collection of Czechoslovak Chemical Communications
- Vol. 64 (6) , 1013-1027
- https://doi.org/10.1135/cccc19991013
Abstract
Three new, substituted, nido carboranes, 7,8-Ph2-10-(SMe2)-7,8-nido-C2B9H10 (1a), 7,8-Ph2-10- (SMeEt)-7,8-nido-C2B9H10 (1b) and 7,8-Ph2-10-(SEt2)-7,8-nido-C2B9H10 (1c) have been synthesised and characterised, including a crystallographic study of the first. Deprotonation of 1a followed by treatment with (MeCN)2(CO)2MoBr(η-C3H5) at 0 °C affords the non-icosahedral 1,2-Ph2-4-(SMe2)-5-(η-C3H5)-5,5-(CO)2-5,1,2-closo-MoC2B9H8 (2a), which on subsequent warming transforms into icosahedral 2,8-Ph2-5-(SMe2)-1-(η-C3H5)-1,1-(CO)2-1,2,8-closo- MoC2B9H8 (3a). It is argued that under the conditions of these rearrangements the B-S bond is likely to remain intact, and consequently that the identity of the SMe2-labelled boron atom in 3a affords useful experimental information on the course of the isomerisation.Keywords
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