Investigation of Thiaborane closo–nido Conversion Pathways Promoted by N‑Heterocyclic Carbenes

The 12-X-closo-SB11H10 (X = H or I) thiaboranes react with one or two molar equivalents of various N-heterocyclic carbenes (NHCs) to give the deprotonated 12-vertex species of [12-X-SB11H9·NHC]−[NHC-H]+composition as kinetic products. The use of one molar equivalent of a sterically more hindered NHC...

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Published in:Inorganic chemistry 2019-02, Vol.58 (4), p.2471-2482
Main Authors: Vrána, Jan, Holub, Josef, Růžičková, Zdeňka, Fanfrlík, Jindřich, Hnyk, Drahomír, Růžička, Aleš
Format: Article
Language:English
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Summary:The 12-X-closo-SB11H10 (X = H or I) thiaboranes react with one or two molar equivalents of various N-heterocyclic carbenes (NHCs) to give the deprotonated 12-vertex species of [12-X-SB11H9·NHC]−[NHC-H]+composition as kinetic products. The use of one molar equivalent of a sterically more hindered NHC reactant leads to the formation of 12-X-SB11H10·NHC adducts with a heavily distorted cage and the nido electron count. Further reaction of 12-I-SB11H10·NHC to deboronated 12-X-SB10H9·NHC proceeds in acetone to complete the closo–nido reaction pathway under the thermodynamic control. The structures of all compounds have been investigated by NMR spectroscopy and diffraction techniques. The results are supported by theoretical methods.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b03037