Geometrical Characteristics and Atomic Charge Variations of Pd(II) Complexes [Pd(L)Cl2] with an Axial (Pd

Bulletin of the Korean chemical society

Jong Keun Park¹  Yong Guk Cho¹  Bong Gon Kim¹  Shim Sung Lee¹ 

关键词: Atomic charge;    Oxathia macrocycle;    Density functional theory;    Pd(II) complex;    Axial (Pd-O) interaction;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Geometrical structures of [Pd(L)Cl₂] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)Cl2 complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (PdO) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial (PdO) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via �?-acceptors of the empty d-orbitals.

【 授权许可】

Unknown