Theoretical study on the structure and formation mechanism of [C 6 H 5 M m ] − (MAg, Au; m = 1–3)

The structures and formation mechanisms of the important intermediate phenyl‐coinage metal complexes [C 6 H 5 M m ] − (MAg, Au, m = 1–3) are investigated at B3LYP//6‐311G(d, p)/Lanl2dz level using Gaussian 03 program. The adiabatic electron affinity and vertical dissociation energy of [M m ] − and [C 6 H 5 M m ] − are calculated, which are excellently coincident with the experimental determination. The C 6 H 5 group bonds on metal clusters through MC σ bond in the complex [C 6 H 5 M m ] − . The complexes [C 6 H 5 M m ] − (MAg, Au; m = 2–3) are generated through a stepwise reaction. The first step is a direct insertion reaction between [M m ] − (MAg, Au, m = 1–3) and C 6 H 6, which leads to the generation of intermediate [C 6 H 5 M m H] − ( m = 1–3) with the activation and cleavage of CH bond. The second step is the neutral metal atom abstracting the H atom to yield the product [C 6 H 5 M m ] − . © 2008 Wiley Periodicals, Inc. J Comput Chem 2008