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Reaction Control of Dynamic Complexes Relevant to Catalysis

与催化相关的动态配合物的反应控制

基本信息

批准号：
14078222
负责人：
OZAWA Fumiyuki
金额：
$ 26.11万
依托单位：
Kyoto University (2003-2006)Osaka City University (2002)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

(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

(1)1，2-二芳基-3，4-二膦环丁烯(DPCBY)是一种低配位磷化合物，对过渡金属具有极强的x-受体作用。研究了几种含DPCBY配体的有机钯(II)和铂(II)配合物的结构和催化性能。DPCB-Y配位的钯配合物提供了迄今未知的反应性和选择性的高效催化。典型的例子包括苯胺和活性亚甲基化合物与烯丙醇的脱水烯丙基化，烯丙基酯的脱烯丙基，芳基卤化物的胺化和氰化，以及烯酮的氢酰胺化。(2)含DPCB-Y配体的二氯铀络合物能有效地催化二乙撑芳烃与HSiMe2Ph的立体选择性硅氢化反应，得到(Z，Z)-双(2-硅乙烯基)芳烃，它们在立体专一性…中与NBS发生溴代脱硅反应(Z，Z)-双(2-溴乙烯基)芳烃具有较高的几何纯度(&gt；98%)。这些产物是合成几何纯的全顺式聚芳亚乙烯S(PAV)的良好原料，在溶液和固体中都能快速地光异构化成反式PAV。这一现象已被应用于在石英衬底上直接制作微尺度的PAV图案化。(3)含较重硫族原子的Fischer型Ru卡宾RuCl_2(=Cher)(Pcy_3)_2(E=S，Se，Te)催化降冰片烯衍生物与烯基硫化物的开环/交叉易位反应，得到高选择性的异双官能化聚降冰片烯。(4)含大体积膦配体RuCl_2(=C=CHPh)L_2(L=PPR^I，Te)在N-甲基吡咯烷存在下，制备了具有不对称杂原子配体顺铂(Er_N)(Er_M)(Pme_2Ph)_2(E，E‘=B，Si，Ge，Sn)的铂配合物，并通过动力学实验考察了它们的催化活性。反应活性顺序为：PT-B&GT；铂-硅&GT；铂-锡&GT；铂-锗。研究了C-B、C-Si和C-Ge从铂(II)中心还原消除的机理。较少