On the mechanism of homogeneous Pt-catalysis: A theoretical view

Abstract

This review is organized to reveal the recent advances in the theoretical investigation of Pt-catalysed organic transformations, which is sorted by the activated species, including C–H activation, alkyne activation, alkene activation, and allene activation. • Mechanistic studies related of Pt-catalyzed organic transformation. • Mechanism discussions are classified according to the substrates. • Theoretical studies revealed that the mechanism mainly related to the Pt complexes. • The understanding of mechanism would be helpful for further design new Pt-catalysis. Over the past few decades, platinum has attracted remarkable attention and played an important role in promoting construction of C–X (X = C, O, N, B, etc.) bonds in organometallic chemistry. However, understanding the general principle of Pt chemistry is still an urgent task both experimentally and theoretically. Differing from other metals in the same group, such as Ni and Pd, Pt-mediated C–H activation processes mainly involve oxidative addition, σ-complex assisted metathesis, outersphere electrophilic deprotonation, and even carbene Pt complex insertion rather than concerted metalation–deprotonation. In some other catalysis, Pt possesses a strong Lewis acid property to activate a wide range of unsaturated substrates. In this review, the mechanistic principles and recent advancements of various types of Pt-mediated organic molecular activations, including C–H activation, alkyne activation, alkene activation, and allene activation, are systematically summarized from a theoretical viewpoint. These activations generally result in Pt–C bond formation, which can be further transformed for construction of new C–C and C–heteroatom bonds.