PdII([9]aneB2A)L2 配合物中的轨道相互作用和电子密度转移：理论方法。

Orbital interaction and electron density transfer in PdII([9]aneB2A)L2 complexes: theoretical approaches.

机构信息

Department of Chemistry Education and Research Institute of Natural Science, Educational Research Institute Teachers College, Gyeongsang National University, Jinju 660-701, Korea.

出版信息

Molecules. 2013 Oct 14;18(10):12687-706. doi: 10.3390/molecules181012687.

DOI:10.3390/molecules181012687

PMID:24129277

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6270109/

Abstract

The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl-}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the electron-rich trans L-ligand to the low-lying unfilled a1g(5s)-orbital of PdL2 were investigated using B3P86/lanl2DZ for Pd and 6-311+G** for other atoms. The pentacoordinate endo-[Pd([9]aneB2A)(L-donor)2]2+ complex with an axial (soft A--Pd) quasi-bond was optimized for stability. The fifth (soft A--Pd) quasi-bond between the σ-donor of soft A and the partially unfilled a1g(5s)-orbital of PdL2 was formed. The pentacoordinate endo-Pd([9]aneB2A)(L-donor)2]2+ complex has been found to be more stable than the corresponding tetracoordinate endo-Pd complexes. Except for the endo-Pd pentacoordinates, the tetracoordinate Pd([9]aneBAB)L2 complex with one equatorial (soft A-Pd) bond is found to be more stable than the Pd([9]aneB2A)L2 isomer without the equatorial (A-Pd) bond. In particular, the geometric configuration of endo-[Pd([9]anePNP)(L-donor)2]2+ could not be optimized.

摘要

钯配合物{ Pd([9]aneB2A)L2 和 Pd([9]aneBAB)L2，其中 A = P，S； B = N； L = PH3，P(CH3)3，Cl-}的几何结构，它们对轴向或轴向（软 A…Pd）配位的选择性轨道相互作用[9]aneB2A 三齿与 PdL2 配位，以及富电子反式 L-配体向 PdL2 的低能未占据 a1g(5s)-轨道的电子密度转移，使用 B3P86/lanl2DZ 进行 Pd 和 6-311+G**进行其他原子的研究。优化了具有轴向（软 A--Pd）准键的五配位内-[Pd([9]aneB2A)(L-供体)2]2+配合物，以达到稳定性。软 A 的σ供体与 PdL2 的部分未填充 a1g(5s)-轨道之间形成了第五个（软 A--Pd）准键。已发现五配位内-[Pd([9]aneB2A)(L-供体)2]2+配合物比相应的四配位内-Pd 配合物更稳定。除了内-Pd 五配位物外，还发现具有一个赤道（软 A-Pd）键的四配位 Pd([9]aneBAB)L2 配合物比没有赤道（A-Pd）键的 Pd([9]aneB2A)L2 异构体更稳定。特别是，内-[Pd([9]anePNP)(L-供体)2]2+的几何构型无法进行优化。