A Comparative Review of Computational Methods as Applied to Gold(I) Complexes and Mechanisms

Abstract

In the last two decades, the field of homogeneous gold catalysis has been extremely active, growing at a rapid pace. Another rapidly-growing field—that of computational chemistry—has often been applied to the investigation of various gold-catalyzed reaction mechanisms. Unfortunately, a number of recent mechanistic studies have utilized computational methods that have been shown to be inappropriate and inaccurate in their description of gold chemistry. This work presents an overview of available computational methods with a focus on the approximations and limitations inherent in each, and offers a review of experimentally-characterized gold(I) complexes and proposed mechanisms as compared with their computationally-modeled counterparts. No aim is made to identify a “recommended” computational method for investigations of gold catalysis; rather, discrepancies between experimentally and computationally obtained values are highlighted, and the systematic errors between different computational methods are discussed.