Cyclometalated gold(iii) complexes: noticeable differences between (N,C) and (P,C) ligands in migratory insertion

Chemical Science
Jordi SerraDidier Bourissou

Abstract

Gold(iii) complexes are garnering increasing interest for opto-electronic, therapeutic and catalytic applications. But so far, very little is known about the factors controlling their reactivity and the very influence of the ancillary ligand. This article reports the first comprehensive study on this topic. The reactivity of a cationic (N,C) gold(iii) complex, namely 1A, towards ethylene has been thoroughly studied and compared with that of the related (P,C) complex 1C. A cationic gold(iii) complex 5A resulting from double insertion of ethylene was selectively obtained. Complex 5A was found to be remarkably stable. It was trapped with chloride and fully characterized. In marked contrast to that observed with 1C, no β-H elimination or linear-to-branched rearrangement of the alkyl chain occurred with 1A. The energy profile for the reactions of 1A with ethylene has been comprehensively investigated computationally, and the influence of the ancillary ligand has been precisely delineated. Because nitrogen is a weaker donor than carbon (and phosphorus), the (N,C) ligand is very electronically dissymmetric, much more than the (P,C) ligand. This makes the two reactive sites at gold quite different, which noticeably influences the compe...Continue Reading

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Citations

Jun 2, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Charlie BlonsDidier Bourissou
Sep 18, 2018·Chemical Communications : Chem Comm·Marte Sofie Martinsen HolmsenMats Tilset
Jan 30, 2020·Chemistry : a European Journal·Riccardo BonsignoreAngela Casini
May 22, 2020·Angewandte Chemie·Mathilde RigouletDidier Bourissou
Dec 10, 2020·Chemical Communications : Chem Comm·Sara Fernández-MoyanoPablo Espinet
Apr 17, 2021·Chemical Communications : Chem Comm·Harish S KunchurMaravanji S Balakrishna
Jun 30, 2019·Inorganic Chemistry·Sailajah GukathasanSamuel G Awuah

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Methods Mentioned

BETA
column
NMR
X-ray

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