Cyclometalated gold(iii) complexes: noticeable differences between (NC) and (PC) ligands in migratory insertion

摘要

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 competition between migratory insertion and β-H elimination, and actually changes the outcome of the olefin insertion at gold. This study provides valuable insight into the influence of ancillary ligands on gold(iii) reactivity, something critical to further develop Au(iii) and Au(i)/Au(iii) catalysis.