Synthesis and Characterization of a Gold Vinylidene Complex Lacking π‐Conjugated Heteroatoms |
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Authors: | Robert J Harris Prof Ross A Widenhoefer |
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Institution: | French Family Science Center, Duke University, Durham, NC 27708‐0346 (USA) |
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Abstract: | Hydride abstraction from the gold (disilyl)ethylacetylide complex ( P )Au{η1‐C?CSi(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 )Au?C?CSi(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‐C?CSi(Me)2CH2CH2Si (Me)2}]+B(C6F5)4?. |
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Keywords: | bonding modes carbene ligands carbenoids gold vinylidenes |
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