title: Theoretical study on the structure and formation mechanism of [C6H5Mm]- (M=Ag, Au; m=1-3).
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 sigma 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)](-).
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 11602, China.
authors.forename: Xiao-Jing
authors.initials: XJ
authors.lastname: Liu
authors.forename: Chuan-Lu
authors.initials: CL
authors.lastname: Yang
authors.forename: Xiang
authors.initials: X
authors.lastname: Zhang
authors.forename: Ke-Li
authors.initials: KL
authors.lastname: Han
authors.forename: Zi-Chao
authors.initials: ZC
authors.lastname: Tang