DEVELOPMENT OF NEW CHIRAL CATALYSTS

金属配合物在均相不对称催化反应中起着重要的作用。合成了CoX_2（L-L）的含不同双齿膦配体（BINAP，DIOP，CHIRAPHOS）的钴卤配合物，并对其结构进行了表征。[CoX_2P]配合物是由CoCl_3·6H_2O与1当量的H_2O反应制得。二齿膦配体在CH_2Cl_2中的反应。该<31>络合物的1H NMR谱显示在-14.79ppm处的单峰。钴<31>卤配合物的1H NMR化学位移取决于配位膦。化学位移非常接近BINAP配体。[CoCl_2（binap）]的晶体结构为：[CoCl_2（binap）]，<45>C_H_P_2Cl_4Co<34>，单斜晶系，P2_1，a=10.870（4）A，B=13.024（4）A^^，C=14.316（3）A^^，β =99.14（2）A，V=2001（1）A^^，Z=2，R（F）= 4.5%。这种化合物非常稳定，在245-250 ℃下熔化而不分解。合成了含双齿膦配体（BINAP）的卤代镍配合物NiX_2（L-L），在不使用起始催化剂的条件下，对不对称氢化、全氟烷基化和偶联反应进行了研究。

The metal complex is very important in the homogeneous asymmetric catalytic reaction. Accordingly, new chiral metal complexes as catalyst was synthesized.Cobalt halogen complexes of composition CoX_2(L-L) containing different bidentate phosphine ligands (BINAP, DIOP, and CHIRAPHOS) have been prepared and characterized. The [CoX_2P] complexes were obtained from the reaction of CoCl_3ﾟ6H_2O with 1 equiv. of bidentate phosphine ligands in CH_2Cl_2. ^<31>P NMR spectrum of this complex showed a singlet at -14.79 ppm. ^<31>P NMR chemical shift for the cobalt halogen complex depend on the ligated phosphine. The chemical shift is very close to the BINAP ligand. The structures of [CoCl_2(binap)] is determined by X ray crystallography : for [CoCl_2(binap)], C_<45>H_<34>P_2Cl_4Co, monoclinic, P2_1, a=10.870(4) A, b=13.024(4)A^^ﾟ, C=14.316(3)A^^ﾟ, beta=99.14(2)ﾟ, V=2001(1)A^^ﾟ^3, Z=2, R(F)=4.5%. This compound is very stable and melts without decomposition at 245-250 ﾟC. Other related complexes have also been prepared and characterized.Nickel halogen complex of composition NiX_2(L-L) containing bidentate phosphine ligand (BINAP) have also been prepared.No using the initial catalyst for the asymmetric hydrogenation, perfluoroalkylation, and closs coupling reaction have been provided good results.