Development of novel catalytic systems based on cooperative activation by multinuclear active centers

[γ-H_2SiW_<10 bbb_ O_<36>Cu(II)_2(μ-1,1- n_3)_2]^<4->(I)]是一种铜取代γ-Keggin钨酸硅[γ-H_2SiW_<10 bbb_ O_<36>Cu(II)_2(μ-1,1- n_3)_2]^<4->(I)]的预催化剂，可用于烯烃与重氮化合物的化学选择性环丙烷化反应。各种烯烃有效地转化为相应的环丙烷衍生物，收率高。此外，一种新型的二钒取代磷钨酸盐[γ-H_2PV_2W_<10>O_<40>]^<3->(II)能以H_2O_2作为唯一氧化剂催化环烷烃的立体特异性和选择性羟基化反应，对相应醇的选择性≧98%，H_2O_2利用率≧80%。

A dicopper-substituted γ-Keggin silicotungstate, [γ-H_2SiW_<10>O_<36>Cu(II)_2(μ-1,1-N_3)_2]^<4->(I), could act as an efficient precatalyst for the chemoselective cylopropanation of olefins with diazo compounds. Various kinds of olefins were efficiently converted to the corresponding cyclopropane derivatives in good yields. In addition, a novel di-vanadium-substituted phosphotungstate, [γ-H_2PV_2W_<10>O_<40>]^<3->(II), could catalyze the stereospecific and selective hydroxylation of cyclic alkanes with H_2O_2 as a sole oxidant with ≧98% selectivity to the corresponding alcohols and ≧80% efficiency of H_2O_2 utilization.