The ability of Lewis acids to coordinate to transition metals as σ-acceptor ligands was recognized as early as in the 1970's, but so-called Z-type ligands remained curiosities until the early 2000's. Over the last decade, significant progress has been made in this area, especially via the incorporation of Lewis acid moieties into multidentate, ambiphilic ligands. Our understanding of the nature and influence of TM → Z interactions has considerably improved and the scope of Lewis acids susceptible to behave as σ-acceptor ligands has been significantly extended. This feature article summarizes these recent achievements.

The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle involving a sequence of Csp²–X oxidative addition, Csp²–H auration and reductive elimination, allowing a gold-catalyzed direct arylation of arenes with aryl halides. Key to this discovery is the use of Me-Dalphos, a simple ancillary (P,N) ligand, that allows the bottleneck oxidative addition of aryl iodides and bromides to readily proceed under mild conditions. The hemilabile character of the amino group plays a crucial role in this transformation, as substantiated by density functional theory calculations.