Closely Approaching the Silylium Ion (R3Si+).
The crystal structure of the tri-isopropyl silyl species, i-Pr(3)Si(Br(6)-CB(11)H(6)), where the brominated carborane Br(6)-CB(11) H(6)(-) is perhaps the least nucleophilic anion presently known, has revealed the highest degree of silylium cation character (R(3)Si(+)) yet observed. The average C-Si-C angle is 117 degrees , only 3 degrees short of the planarity expected of a pure silylium ion(120 degrees ). This value compares to 114 degrees recently reported for a toluene-solvated silyl cation, [Et(3)Si(toluene)](+) by Lambert and co-workers. The greater silylium ion character of i-Pr(3)Si(Br(6)-CB(11)H(6)) versus [i-Pr(3)Si(toluene)](+) is also reflected in the larger downfield shift of the silicon-29 nuclear magnetic resonance, 109.8 versus </=94.0 parts per million. The unusual bonding of toluene to R(3)Si(+) in Lambert's compound is reinterpreted as a significant covalent pi interaction.
Reed
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CA
Xie
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Bau
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Benesi
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