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

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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