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）已发现1,2-二芳基-3,4-二磷酸烯环丁烯（DPCB-Y）作为低坐标磷化合物，是对过渡金属的极强X接受者。已经检查了几个有机钯（II）和铂（II）的结构和催化特性。 DPCB-Y协调的钯配合物提供了高效的催化剂，具有隐藏的反应性和选择性。代表性的例子包括苯胺和活性亚甲基化合物脱水的脱水，与种植酸盐的脱水，抗原酯的交易，芳基卤化物的胺化和氰化以及烯烃的氢化。 Detailed catalytic mechanisms have been examined for dehydrative allo- allation 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以立体传感器的方式…以高几何纯度（> 98％）为bis（z，z）-bis（2-溴乙烯基）领域。这些产品是良好的主演材料，用于合成几何纯纯的全盘聚（芳基乙烯基）S（PAVS），它们迅速经历了光异构化，以在溶液和固体中的trans-pavs。这种现象（3）fischer型朗特芬碳纤维含有较重的chalcogen原子rucl_2（= = cher）（pcy_3）_2（e = s，s，se，se，te）催化环烯基衍生物与氯烷基化的高质量构成型hodogenens to horkogenase to hodifififififififififififus to hododifus to hododifus to 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已经制备了具有不对称杂种配体CIS-PT（ER_M）（PME_2PH）_2（E，E，E'= B，SI，GE，SN）的复合物，并通过动力学实验检查了它们对碱插入的反应性。反应性降低：Pt-B> PT-SI> PT-SN> PT-GE。还研究了C-B，C-SI和C-GE减少铂（II）中心消除的机制。较少的