Theoretical study on the structure and formation mechanism of [C6H5Mm]− (MAg, Au; m = 1–3)

✍ Scribed by Xiao-Jing Liu; Chuan-Lu Yang; Xiang Zhang; Ke-Li Han; Zi-Chao Tang

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 627 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20926

✦ Synopsis

Abstract

The structures and formation mechanisms of the important intermediate phenyl‐coinage metal complexes [C~6~H~5~M~m~]^−^ (MAg, 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 MC σ bond in the complex [C~6~H~5~M~m~]^−^. The complexes [C~6~H~5~M~m~]^−^ (MAg, Au; m = 2–3) are generated through a stepwise reaction. The first step is a direct insertion reaction between [M~m~]^−^ (MAg, 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 CH 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