Synthesis and Characterization of a Gold Vinylidene Complex Lacking π‐Conjugated Heteroatoms1. Issue 23 (23rd April 2015)

• Record Type: Journal Article
• Authors: Harris, Robert J.; Widenhoefer, Ross A.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 23(2015)
• Page Start: 6867
• Page End: 6869
• Publication Date: 2015-04-23
• Subjects: bonding modes -- carbene ligands -- carbenoids -- gold -- vinylidenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201501474
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hydride abstraction from the gold (disilyl)ethylacetylide complex [(P )Au{η 1 ‐CCSi(Me)2 CH2 CH2 SiMe2 H}] (P =P( t Bu)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 (Δ G ≠ =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 − . Abstract : Good as gold : Cationic gold (β, β‐disilyl)vinylidene complex1 was generated by addition of a pendant silylium ion to the CC bond of a gold acetylide complex (see scheme, P =P t Bu2 ( o ‐biphenyl)). The vinylidene C1 and C2 atoms of1 undergo facile interconversion, presumably via a π‐disilacyclohexyne intermediate. 29 Si NMR analysis of1 indicates delocalization of positive charge onto both the β‐silyl groups and the (P )Au fragment.