Studies on Syntheses and Reactivities of New Transition Metal Phosphine Complexes

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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.