| Project/Area Number |
14078222
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kyoto University (2003-2006)
Osaka City University (2002) |
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Principal Investigator |
OZAWA Fumiyuki Kyoto University, Institute for Chemical Research, Profpssor, 化学研究所, 教授 (40134837)
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| Co-Investigator(Kenkyū-buntansha) |
OKAZAKI Masaaki Kyoto University, Institute for Chemical Research, Associate Professor(April 2005-March 2006), 化学研究所, 助教授 (20292203)
KATAYAMA Hiroyuki Kyoto University, Institute for Chemical Research, Assistant Professor(April 2005-March 2006), 化学研究所, 助手 (50315975)
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| Project Period (FY) |
2002 – 2005
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥40,800,000 (Direct Cost: ¥40,800,000)
Fiscal Year 2005: ¥9,600,000 (Direct Cost: ¥9,600,000)
Fiscal Year 2004: ¥9,600,000 (Direct Cost: ¥9,600,000)
Fiscal Year 2003: ¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2002: ¥8,300,000 (Direct Cost: ¥8,300,000)
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| Keywords | Catalytic Intermediates / Dynamic Control / Highly Efficient Catalysis / Palladium Complexes / Platinum Complexes / Ruthenium Complexes / Low-coordinate Phosphorus Ligands / Heteroatom Ligands / ビニル(シリル)白金錯体 / ビニリデンルテニウム錯体 / ジホスフィニデンシクロブテン / (π-アリル)パラジウム錯体 / ジカチオン性パラジウム錯体 / 脱水環化反応 / ヒドロシリル化反応 / 共役付加反応 / ゲルミル(スタニル)白金錯体 / ビス(ゲルミル)白金錯体 / 脱アリル化触媒 / ヒドロシリル化触媒 / アセチレン共二重化触媒 / ヒドリド白金錯体 / ヒドリドパラジウム錯体 / C-O結合切断反応 / アリル化触媒反応 / 開環メタセシス重合 / 末端官能基化ポリマー / シリル白金錯体 / アリルアルコール / カルベンルテニウム錯体 / 開環メタセシス錯体 / シリル(ボリル)白金錯体 |
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| Research Abstract |
(1)1,2-Diaryl-3,4-diphosphinidenecyclobutenes (DPCB-Y) as low-coordinate phosphorus compounds have been found to serve as extremely strong x-acceptors towards transition metals. Structures and catalytic properties of several organo- palladium(II) and-platinum(II) complexes bearing DPCB-Y ligands have been examined. The DPCB-Y-coordinated palladium complexes provide highly efficient catalysis with hitherto unknown reactivity and selectivity. Representative examples include dehydrative allylation of aniline and active methylene compounds with allylic alcohols, deallylation of allylic esters, amination and cyanation of aryl halides, and hydroamidation of enones. Detailed catalytic mechanisms have been examined for dehydrative allylation of aniline.
(2)Dichlororuthenium(II) complexes bearing DPCB-Y ligands efficiently catalyze stereoselective hydrosilylation of diethynylarenes with HSiMe2Ph to afford (Z,Z)-bis(2-silylethenyl)arenes, which undergo bromodesilylation with NBS in a stereospecif
… More
ic manner giving (Z,Z)-bis(2-bromoethenyl)arenes in high geometrical purity (>98%). The products are good staring materials for the synthesis of geometrically pure all-cis poly(arylene vinylene)s (PAVs), which rapidly undergo photoisomerization to trans-PAVs both in solution and in the solid. This phenomenon has been applied to direct microscale patterning of PAVs onto a quartz substrate.
(3)The Fischer-type ruthenium carbenes bearing heavier chalcogen atoms RuCl_2(=CHER)(PCy_3)_2 (E = S, Se, Te) catalyze ring-opening/cross-metathesis of norbornene derivatives with alkenyl chalcogenides to give heterodifunctionalized poly(norbornenes) in high selectivities.
(4)The vinylideneruthenium complexes bearing bulky phosphine ligands RuCl_2(=C=CHPh)L_2 (L = PPr^i, PCy_3) serve as good catalyst precursors for (Z)-selective cross-dimerization between arylacetylenes and silylacetylenes in the presence of N-methylpyrrolidine.
(5)The platinum complexes having unsymmetrical heteroatom ligands cis-Pt(ER_n)(ER_m)(PMe_2Ph)_2 (E, E' = B, Si, Ge, Sn) have been prepared, and their reactivity towards alkyne-insertion has been examined by kinetic experiments. The reactivity decreases in the order : Pt-B > Pt-Si > Pt-Sn > Pt-Ge. The mechanisms of C-B, C-Si, and C-Ge reductive elimination from platinum(II) centers have also been investigated. Less
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