Mechanistic Study of Alkyne Insertion into Cu-Al and Au-Al Bonds: A Paradigm Shift for Coinage Metal Chemistry.

ABSTRACT: In this work, the mechanism of the insertion reaction of 3-hexyne into Cu-Al and Au-Al bonds in M-aluminyl (M = Cu, Au) complexes is computationally elucidated. The mechanism is found to be radical-like, with the Cu-Al and Au-Al bonds acting as nucleophiles toward the alkyne, and predicts a less efficient reactivity for the gold-aluminyl complex. The proposed mechanism well rationalizes the kinetic (or thermodynamic) control on the formation of the syn (or anti) insertion product into the Cu-Al bond (i.e., dimetallated alkene) which has been recently reported. A comparative analysis of the electronic structure reveals that the reduced reactivity at the gold site─usually showing higher efficiency than copper as a "standard" electrophile in alkyne activation─arises from a common feature, i.e

SUBMITTER: Sorbelli D 

PROVIDER: S-EPMC9795551 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature