Publisher： John Wiley & Sons Inc
E-ISSN： 1521-3773|54|23|6867-6869
ISSN： 1433-7851
Source： ANGEWANDTE CHEMIE INTERNATIONAL EDITION, Vol.54, Iss.23, 2015-06, pp. : 6867-6869
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Abstract
AbstractHydride abstraction from the gold (disilyl)ethylacetylide complex [(P)Au{η1‐CCSi(Me)2CH2CH2SiMe2H}] (P=P(tBu)2o‐biphenyl) with triphenylcarbenium tetrakis(pentafluorophenyl)borate at −20 °C formed the cationic gold (β,β‐disilyl)vinylidene complex [(P)AuCCSi(Me)2CH2CH2Si(Me)2]+B(C6F5)4− with ≥90 % selectivity. 29Si NMR analysis of this complex pointed to delocalization of positive charge onto both the β‐silyl groups and the (P)Au fragment. The C1 and C2 carbon atoms of the vinylidene complex underwent facile interconversion (ΔG≠=9.7 kcal mol−1), presumably via the gold π‐disilacyclohexyne intermediate [(P)Au{η2‐CCSi(Me)2CH2CH2Si(Me)2}]+B(C6F5)4−.
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