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Synthesis and Characterization of a Gold Vinylidene Complex Lacking π‐Conjugated Heteroatoms
Author(s) -
Harris Robert J.,
Widenhoefer Ross A.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201501474
Subject(s) - heteroatom , conjugated system , characterization (materials science) , chemistry , materials science , organic chemistry , nanotechnology , ring (chemistry) , polymer
Hydride abstraction from the gold (disilyl)ethylacetylide complex [( P )Au{η 1 ‐CCSi(Me) 2 CH 2 CH 2 SiMe 2 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 )AuCCS i(Me) 2 CH 2 CH 2 Si (Me) 2 ] + B(C 6 F 5 ) 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 ‐ CCSi(Me) 2 CH 2 CH 2 Si (Me) 2 }] + B(C 6 F 5 ) 4 − .