Studies on Syntheses and Reactivities of New Transition Metal Phosphine Complexes

1.合成了20个新的&lt；[COX_2(P-P)_2]^(n+)&gt；型配合物，其中P-P代表1，2-或1，3-双膦配体。对于&lt；[Co(O_2)(P-P)_2]^+&gt；和&lt；[CoCl2(P-P)_2]^+&gt；，配位&lt；O_2&gt；分子的反应性和顺式二氯配合物的异构化速率与P-P配体的空间因子有关。研究了四齿膦配体&lt；[Co(L)(P-P)_2](n+)&gt；(L=双齿配体)的热稳定性。Pr_2&gt；和&lt；nh_2&gt；&lt；chrch_2&gt；P(&lt；C_6&gt；&lt；H_5&gt；)&lt；CH_2&gt；&lt；CH_2&gt；P(&lt；C_6&gt；&lt；H_5&gt；)&lt；CH_2&gt；(R=H，&lt；CH_3&gt；)或&lt；C6&gt；&lt；H5&gt；)。通过X-射线分析、核磁共振、吸收光谱和圆二色谱对其结构进行了表征。所有这些四齿膦配合物都立体选择性地形成了一种特定的几何或光学异构体。

1. Twenty new complexes of the <[CoX_2(P-P)_2]^(n+)> type were prepared, where P-P represents 1,2- or 1,3-diphosphine chelates. For <[Co(O_2)(P-P)_2]^+> and <[CoCl_2(P-P)_2]^+> , the reactivity of the coordinated <O_2> molecule and the isomerization rates of the cisdichloro complexes was correlated to the steric factor of P-P ligands. The thermal stability of <[Co(L)(P-P)_2]^(n+)> (L = bidentate ligands) was examined and found to be depend on the kind of coordinating atoms of L. 2. Forty new cobalt( <III> ) complexes containing a quadridentate phosphine ligand of the types <R_2> <PCH_2> <CHRNHCH_2> <CH_2> <NHCHRCH_2> <PR_2> and <NH_2> <CHRCH_2> P( <C_6> <H_5> ) <CH_2> <CH_2> P( <C_6> <H_5> ) <CH_2> <CHRNH_2> (R = H, <CH_3> or <C_6> <H_5> ) were prepared. The structure of the complexes was determined by means of X-ray analysis, NMR, absorption and circular dichroism spectra. All of these quadridentate phosphine complexes formed stereoselectively a particular geometrical or optical isomer.