确定溶液配合物顺反异构体构型的新方法

A NEW METHOD OF DETERMINING THE CONFIGURATION OF GEOMETRICAL CIS,TRANS-ISOMERS OF COMPLEXES IN SOLUTION

本文首次提出了确定溶液含二齿配体的配合物几何顺反异构体构型的新方法,定义了三元配合物MLL′(或ML_2)中ML与ML′(或ML)二跃迁偶极矩分向量之间的夹角θ,作为该配合物中配体L与L′(或L)之间几何因子的量度,当θ≤90°,为顺式异构体;当θ≥120°,为反式异构体;当90°<0<120°,居于顺反异构体之间。我们把单齿配体配合物顺反异构体的定义推广到含两个二齿配体的配合物。而且对配合物内配体之间的空间相对位置作了近似定量化的描述。

A new method of determining the configuration of geometrical cis, trans-isomers is proposed for the first time in this paper. The transition moments of the complexes are calculated with the correspondent exrerimental data of multiwavelength spectroscopic mcasurements cited from the related references. On the basis of the two postulations, the angle of θ between the two partial vectors of the transition moments p_(ml) and p_(ml)' in a ternary complex MLL' is defined as a measure of the geometrical factor between the ligands L and L' in the ternary complex MLL'. For cis-isorner, θ≤90°; for transisomer, θ≥120°; when 90°<θ<120°, the configuration of the geometrical isomer is in a state of the middle of cis, trans-isomers. The definition of cis, trans-isomers for monodentate ligands has been extended to complexes containing two bidentate ligands. The relative position between two ligands in space of a complex can be approximately quantitatively described with the angle of θ.