Synthesis and Characterization of a Gold Vinylidene Complex Lacking π-Conjugated Heteroatoms.

Journal Article

Hydride abstraction from the gold (disilyl)ethylacetylide complex [(P)Au{η(1) -CCSi(Me)2 CH2 CH2 SiMe2 H}] (P=P(tBu)2 o-biphenyl) with triphenylcarbenium tetrakis(pentafluorophenyl)borate at -20 °C formed the cationic gold (β,β-disilyl)vinylidene complex [(P)AuCCSi(Me)2 CH2 CH2 Si(Me)2 ](+) B(C6 F5 )4 (-) with ≥90 % selectivity. (29) Si 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{η(2) -CCSi(Me)2 CH2 CH2 Si(Me)2 }](+) B(C6 F5 )4 (-) .

Full Text

Duke Authors

Cited Authors

  • Harris, RJ; Widenhoefer, RA

Published Date

  • June 2015

Published In

Volume / Issue

  • 54 / 23

Start / End Page

  • 6867 - 6869

PubMed ID

  • 25908213

Electronic International Standard Serial Number (EISSN)

  • 1521-3773

International Standard Serial Number (ISSN)

  • 1433-7851

Digital Object Identifier (DOI)

  • 10.1002/anie.201501474

Language

  • eng