| Project/Area Number |
09309006
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| Research Category |
Grant-in-Aid for Scientific Research (A).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
広領域
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| Research Institution | Osaka University |
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Principal Investigator |
TANI Kazuhide Osaka University, Graduate School of Engineering Science, Professor, 基礎工学研究科, 教授 (60029444)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAGATA Tsuneaki Osaka University, Graduate School of Engineering Science, Research Associate, 基礎工学研究科, 助手 (70166594)
KATAOKA Yasutaka Osaka University, Graduate School of Engineering Science, Lecturer, 基礎工学研究科, 講師 (90221879)
MASHIMA Kazushi Osaka University, Graduate School of Engineering Science, Associate Professor, 基礎工学研究科, 助教授 (70159143)
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| Project Period (FY) |
1997 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 2000: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1999: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1998: ¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 1997: ¥20,200,000 (Direct Cost: ¥20,200,000)
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| Keywords | iridium / rhodium / tantalum / P-N ligand / stereospecific methyl migration / C-H activation / O-H activation / MMA polymerization / ジルコニウム / ハフニウム / MMA / 重合触媒 / パーアリールホスフィン / 水素移動型 / Cp'-P配位子 / 立体特異的 / モノアザジエン / パーアリールジホスフィン配位子 / カチオン錯体 / メタノールの活性化 / キレート / 面不斉 / ジアザジエン / 極性モノマー / パ-アリールジホスフィン / バナジウム / 炭素-炭素結合切断反応 / 4級炭素化合物 / 超原子価化合物 / Tp^* |
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| Research Abstract |
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 provided
4) 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
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