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Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐ closo ‐dodecaborane(12) Derivatives
Author(s) -
Wrackmeyer Bernd,
Klimkina Elena V.,
Milius Wolfgang
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200027
Subject(s) - silylation , chemistry , trimethylsilyl , carborane , reactivity (psychology) , carbene , crystallography , stereochemistry , medicinal chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
Non‐cyclic and cyclic silyl‐substituted 1, 2‐dicarba‐ closo ‐dodecaborane(12) derivatives were prepared mainly by salt elimination methods. Several known and new compounds were structurally characterized by X‐ray analysis in the solid state and by mulinuclear magnetic resonance ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR) in solution. This includes the 1, 2‐bis(trimethylsilyl) and 1, 2‐bis(chlorodimethylsilyl) derivatives as examples for non‐cyclic compounds and a series of 1, 1, 3, 3‐tetramethyl‐4, 5‐[1, 2‐dicarba‐ closo ‐dodecaborano(12)]‐1, 3‐disila‐2‐element‐cyclopentanes (element = S, Se, Te). Numerous spin‐spin coupling constants were determined together with their signs. Molecular gas phase geometries for most compounds studied were optimized by calculations [B3Lyp/6‐311+G(d, p)], and NMR parameters were calculated at the same level of theory. The conversion of silyl‐substituted ortho ‐carboranes into their respective 7, 8‐dicarba‐ nido ‐undecaborate(1‐) derivatives was explored successfully for several examples.