Study on Transition-Metal Complexes with Multi-Element Ligands

该项目的目的是创建具有第13至16族元素配体的过渡金属络合物的新化学。在配位圈中具有两个或两个以上典型元素的过渡金属配合物也参与了这个项目。所得结果如下所示。磷化物配合物的研究：制备了含磷化物侧链的锆和铪配合物。发现这些配合物通过与MMAO.2组合用作乙烯聚合和乙烯/苯乙烯共聚的催化剂。有机腈的C-C键断裂：发现铁甲硅烷基络合物具有断裂有机腈的C-C键的能力。理论计算表明了合理的反应途径。建立了裂解有机腈C-C键的催化循环，并提出了反应机理.铁催化的醛和酮的硅烷基氰化反应：醛或酮的硅烷基氰化反应在无水乙醇溶液中进行。 ...更多信息 在催化量的铁甲基络合物存在下，Et_3SiH与MeCN光反应生成Et_3SiCN。从起始铁络合物衍生的一些铁络合物充当MeCN的C-C键断裂和伴随的Si-C键形成以及甲硅烷基氰化中的Si-C键断裂的催化剂。亚磷硼配合物的研究：在BH_3-P（OMe）（NMeCH_2）_2存在下，钼的甲基配合物发生光反应，生成亚磷硼钼配合物。配合物与MeI和PMe_3反应，分别发生Mo-B和B-P键断裂，热反应导致B-H键断裂.亚磷酸膦配合物的研究：钼与两个或三个二氨基取代的亚磷酸根的配合物与TMSOTf反应，得到相应的阳离子亚磷酸膦配合物。X-射线结构分析和核磁共振谱表明了优先的非桥连结构。DFT计算已被纳入研究的优先权的非桥接形式的膦亚磷酸盐配合物，连同优先权的桥接形式的类似的亚甲硅烷基烷氧基甲硅烷基配合物。少

The purpose of this project is to create new chemistry of transition metal complexes with a group 13 to 16 element ligand. Transition metal complexes with two or more typical elements in the coordination sphere are also involved in this project. The results obtained are shown below.1. A study on phosphide complexes :Some Zr and Hf complexes with a phosphide-pendant cyclopentadienyl ligand have been prepared. These complexes were found to serve as catalyst for ethylene polymerization and ethylene/stylene copolymerization by a combination with MMAO.2. C-C bond cleavage of organonitriles :An iron silyl complex was found to have the ability to cleave a C-C bond of organonitriles. The theoretical calculation suggested a reasonable reaction pathway. The catalytic cycle to cleave a C-C bond of organonitriles could be established and the reaction mechanism was proposed.3. Iron-catalyzed silylcyanation of aldehyde and ketone :Silylcyanation of aldehyde or ketone was performed in a solution invo … More lving Et_3SiCN produced by photoreaction of Et_3SiH with MeCN in the presence of a catalytic amount of an iron methyl complex. Some iron complex derived from the starting iron complex serves as a catalyst both for C-C bond cleavage of MeCN and concomitant Si-C bond formation and for Si-C bond cleavage in silylcyanation.4. A study on phosphiteboryl complexes :The photoreaction of an Mo methyl complex in the presence of BH_3-P(OMe)(NMeCH_2)_2 produced the phosphiteboryl Mo complex. The complex reacts with MeI and PMe_3 with Mo-B and B-P bond cleavage, respectively, and its thermal reaction leads to B-H bond cleavage.5. A study on phosphenium phosphite complexes :Mo complexes with two or three diamino-substituted phosphite react with TMSOTf to give the corresponding cationic phosphenium phosphite complexes. The X-ray structure analyses and the NMR spectra showed the preferential nonbridging structure. DFT calculations have been incorporated to study the preference of the nonbridging form for phosphenium phosphite complexes, together with the preference of the bridging form for the analogous silylene alkoxysilyl complex. Less