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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 1，2-二芳基-3，4-二磷杂环丁烯（DPCB-Y）作为低配位的磷化合物，对过渡金属离子具有极强的X受体活性。研究了几种含二氯联苯-钇配体的有机钯（Ⅱ）和铂（Ⅱ）配合物的结构和催化性能。DPCB-Y配位钯配合物提供了迄今未知的反应性和选择性的高效催化。代表性实例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化、芳基卤化物的胺化和氰化以及烯酮的氢化酰胺化。研究了苯胺脱水烯丙基化反应的催化机理。（2）含DPCB-Y配体的二氯钌（II）配合物催化二乙炔基芳烃与HSiMe_2 Ph的硅氢加成反应，得到（Z，Z）-双（2-硅基乙烯基）芳烃，后者与NBS发生溴代脱硅反应，产物经溴代脱硅反应生成（Z，Z）-双（2-硅基乙烯基）芳烃，产物经溴代脱硅反应生成（Z，Z）-双（2-硅基乙烯基）芳烃。 ...更多信息合成了高几何纯度（>98%）的（Z，Z）-双（2-溴乙烯基）芳烃。该产物是合成几何纯的全顺式聚芳撑乙烯（PAVs）的良好起始原料，PAVs在溶液和固体中均能快速光异构化为反式PAVs。这种现象已被应用于直接在石英衬底上的PAV的微尺度图案化。（3）带有重硫族元素RuCl_2（=CHER）（PCy_3）_2（E = S，Se，Te）的Fischer型钌卡宾催化烯基硫族化合物开环/交叉复分解反应，高选择性地合成了杂双官能化聚烯。（4）含大体积膦配体RuCl_2（=C=CHPh）L_2（L = PPr_1，PCy_3）的亚乙烯基钌配合物是N-甲基吡咯烷存在下芳基乙炔和硅基乙炔（Z）-选择性交叉二聚反应的良好催化剂前体。（5）合成了具有不对称杂原子配体cis-Pt（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炔插入反应活性。反应活性依次为：Pt-B > Pt-Si > Pt-Sn > Pt-Ge。C-B，C-Si和C-Ge还原消除铂（II）中心的机制也进行了研究。少