Development of Selective Organic Synthesis and Catalysis Based on Characteristics of Organotransition Compounds

为了根据有机过渡金属化合物的特性发现新的有机合成和催化作用，我们开展了这一研究项目。得到了以下新结果：1)中性的Ir双膦配合物[IrCl(双膦)]_2能很容易地激活醇、水等的O-H键，生成它们的氧化加成产物。2)低价钒(II)化合物是选择性烷基化、烯丙化、生成C-C键并伴随C-O键断裂的有效试剂。3)合成配合物TP^*MCL_NL_O{TP^*=氢化(吡唑基)硼酸盐，M=第4-6族过渡金属}。提供了(R=烷基)作为TP^*转移试剂4)新的光学活性Cp‘-P配体，包含带有光学活性取代基的吲基和…合成了一个亚烷基连接的二苯基膦基团，并制备了其立体选择性的调节PANAR和中心手性的Rh配合物。建立了以(Cp‘-P)Rh(CO)为催化剂，乙炔、CO、甲基碘化物和三甲基铝选择性合成α，β-不饱和酮的理论催化循环。5)合成了含二苯基膦和2-吡啶基的含氧烷基的配位柔性P-N配体。利用P-N配体的Ir络合物实现了C(sp^3)-H键的可逆氧化加成和还原消除的直接观察。6)合成了一系列1，4-二氮二烯的Nb和Ta的配合物。通过选择辅助配体，1，4-二氮二烯可以与几种不同配位构型的金属配位，平面σ^2，俯卧和仰卧非平面σ^2，π-二胺。PMMA的韧性和多分散性是可以调节的。较少

With the aim of discovering new organic synthesis and catalysis based on characteristics of organotransition metal compounds we performed the research project. The following new results were obtained.1) Neutral iridium diphosphine complexes carrying peraryldiphosphines, [IrCl (diphosphine)]_2, can activate easily O-H bonds of alcohol, water, etc to produce their oxidative addition products. The complex is an efficient catalyst for transfer hydrogenation of unsaturated compounds using methanol as a hydrogen donor.2) Low valent vanadium(II) compounds are useful reagents for selective alkylation, allylation, C-C bond formation accompanying C-O bond cleavage of carbonyl compounds.3) General method of preparation of complexes Tp^*MCl_nL_O {Tp^*=hydrotris (pyrazolyl) borates, M=group 4-6 transition metal} using Tp^*SnR_nCl_<3-n> (R=alkyl) as a Tp^* transfer reagent was provided4) New optically active Cp'-P ligands, containing both an indenyl group carrying an optically active substituent and … More a diphenylphosphino group connected by an alkylene spacer, were synthesized and their stereoselective rhodium complexes regulating the panar as well as the central chirality were prepared. A theoretical catalytic cycle for selective formation of α, β-unsaturated ketones from acetylene, CO, methyl iodide and trimethyl aluminum with (Cp'-P)Rh(CO) as a catalyst was established.5) A coordinatively flexible P-N ligand which has a diphenylphosphino group and a 2-pyridyl group connected by an oxaalkylene chain was synthesized. Direct observation of reversible oxidative addition and reductive elimination of C(sp^3)-H bonds was accomplised by using the iridium complexes of the P-N ligand.6) A series of 1,4-diazadiene complexes of niobium and tantalum have been prepared. These complexes becom active catalysts for polymerization of MMA.By choosing ancillary ligands, 1,4-diazadiene can coordinate to a metal in several different coordination geometry, planar σ^2-, prone and supine nonplanar σ^2, π-enediamide. Tacticity and polydispersity of PMMA could be regulated. Less