磷桥联双金属配合物结构优化的量子化学方法研究

采用Hartree-Fock(HF)及密度泛函理论（Density Functional Theory,DFT）方法，在LANL2DZ和CEP-31G基组水平上，对配合物CpW(CO)₂(μ-CO)(μ-PPh₂)Fe(CO)₃(1)和CpW(CO)₃(μ-PPh₂)Fe(CO)₄(2)的结构进行了优化，并将采用不同方法和基组的优化结果与X射线衍射实验数据对照。结果表明，用量子化学方法优化含重金属原子的较大配合物体系的结构是方便可行的，而且DFT方法在此类计算中有更高的准确度。为日后进一步深入开展含有过渡金属原子的双金属配合物的理论研究提供了可靠的计算依据。

Geometry optimizations of bimetallic phosphido-bridged complex CpW (CO) 2 (μ-CO) (μ-PPh2 ) Fe(CO) 3 and CpW(CO) 3 (μ -PPh2) Fe(CO) 4 by quantum chemistry method

Complete geometry optimizations were carried out by Hartree-Fock (HF) and Density Functional Theory (DFT) methods to study the molecular structure of binuclear transition-metal complexes CpW(CO)₂(μ-CO)(μ-PPh₂)Fe(CO)₃(1) and CpW(CO)₃(μ-PPh₂)Fe(CO)₄(2). A comparison of the experimental data and the calculated structural parameters demonstrates that the most accurate geometry parameters are calculated by the MPW1PW91/CEP-31G among the two DFT methods. The result provided a theoretical guidance on detailed study on the binuclear phosphido-bridged complex containing transition metal atoms, which could be useful in the further study of the heterobimetallic phosphido bridged complexes.