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Gold(III) Alkyne Complexes: Bonding and Reaction Pathways
Author(s) -
Rocchigiani Luca,
FernandezCestau Julio,
Agonigi Gabriele,
Chambrier Isabelle,
Budzelaar Peter H. M.,
Bochmann Manfred
Publication year - 2017
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.201708640
Subject(s) - alkyne , chemistry , catalysis , organic chemistry
The synthesis and characterization of hitherto hypothetical Au III π‐alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors. Bonding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of Pt II and their drastically more reactive Au III congeners. Lack of back‐bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C−C bond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as a new reaction sequence in gold chemistry.