Relativistic effects in homogeneous gold catalysis

Abstract

Transition-metal catalysts containing gold present new opportunities for chemical synthesis, and it is therefore not surprising that these complexes are beginning to capture the attention of the chemical community. Cationic phosphine-gold(i) complexes are especially versatile and selective catalysts for a growing number of synthetic transformations. The reactivity of these species can be understood in the context of theoretical studies on gold; relativistic effects are especially helpful in rationalizing the reaction manifolds available to gold catalysts. This Review draws on experimental and computational data to present our current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.

Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes

“…In the last few years there have been amazing developments in gold catalysis (25)(26)(27)(28). Once thought to be a noble metal with little synthetic utility, gold has recently demonstrated its unique and exciting catalytic properties.…”

Homogeneous Gold Catalysis: Mechanism and Relativistic Effects of the Addition of Water to Propyne

“…It has been speculated that the unusual catalytic activity in homogeneous gold catalysis is due to relativistic effects [9]. It is now well known and accepted that gold exhibits unusually large relativistic effects compared to its neighboring atoms in the periodic table, termed the gold maximum of relativistic effects [10,11], which originates mainly from a very large direct relativistic valence 6s-shell contraction [12,13].…”

O2 dissociation in Na-modified gold ultrathin layer on Cu(111)

“…The nature of chemisorbed atomic oxygen on gold is important in elucidating the unique chemistry that has been observed over supported gold catalysts [22,47,48,61,62,64,[158][159][160][161][162][163]. Hence, our finding deserves a particular relevance and claims for further experimental and theoretical work.…”