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

Abstract

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