Theoretical study on the structure and formation mechanism of [C6H5Mm]- (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)](-) (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)](-).
Liu
Xiao-Jing
XJ
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 11602, China.
Yang
Chuan-Lu
CL
Zhang
Xiang
X
Han
Ke-Li
KL
Tang
Zi-Chao
ZC