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Synthesis, Structure, and Reactivity of a Gold Carbenoid Complex That Lacks Heteroatom Stabilization
Author(s) -
Harris Robert J.,
Widenhoefer Ross A.
Publication year - 2014
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.201404882
Subject(s) - chemistry , carbenoid , heteroatom , hydride , reactivity (psychology) , medicinal chemistry , thiocarbamate , cationic polymerization , ligand (biochemistry) , photochemistry , tetrafluoroborate , stereochemistry , crystallography , organic chemistry , alkyl , rhodium , catalysis , medicine , hydrogen , biochemistry , alternative medicine , receptor , ionic liquid , pathology
Hydride abstraction from the neutral gold cycloheptatrienyl complex [( P )Au(η 1 ‐C 7 H 7 )] ( P =P( t Bu) 2 ( o ‐biphenyl)) with triphenylcarbenium tetrafluoroborate at −80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [( P )Au(η 1 ‐C 7 H 6 )] + BF 4 − in 52 % yield, which was characterized in solution and by single‐crystal X‐ray diffraction. This cycloheptatrienylidene complex represents the first example of a gold carbenoid complex that lacks conjugated heteroatom stabilization of the electron‐deficient C1 carbon atom. The cycloheptatrienylidene ligand of this complex is reactive; it can be reduced by mild hydride donors, and converted to tropone in the presence of pyridine N ‐oxide.