An ab inito study on the conformation and gold( I )-gold( I ) interaction of the isomeric H 2C[P(Ph) 2AuX] 2 and HC[P(Ph) 2AuX] 3(X=I,Cl)

Abstract

Ab initio calculations were carried out on the complexes H 2C[P(Ph) 2AuX] 2(X = I,Cl) and HC[P(Ph) 2AuX] 3(X=I,Cl) according to their crystal structures. The potential energy curves of the conformations with respect to the rotations of C-P bonds were generated at MP2 approximate levels, which reveals Au ( I )-Au ( I ) interactions. The calculations show that the Au( I )-Au( I ) interactions exist in all the four complexes with the weak attraction about 10. 0 ∼16. 5 kJ/mol that is close to the estimation of Schmidbaur and the calculation of Pyykkö et al. for other model complexes.

根据配合物H2C[P(Ph)2AUX]2(X=I,CI)和HC[P(Ph)2AUX]3(X=I,CI)的晶体结构对它们进行了从头算研究,在MP2近似水平下得到绕C—P旋转所产生构象的势能曲线,从而揭示AU(I)－AU(I)相互作用. 计算结果表明,在所研究的四个配合物中均存在AU(I)-AU(I)相互作用,该作用较弱,约为10. 0～16. 5kJ/mol,与Schmibaur的实验估计值和Pyykko等对其它模型配合物的计算结果接近.