Study on Transition-Metal Complexes with Multi-Element Ligands

多元素配体过渡金属配合物的研究

• 批准号: 15205010
• 负责人: NAKAZAWA Hiroshi
• 金额: $ 33.2万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15205010/
• 关键词: phosphide complex; C-C bond cleavage; catalytic reaction; silylcyanation; phosphiteboryl complex; phosphenium complex; ホスファイトボラン; B-H結合切断; モリブデン錯体; Mo-B-P結合配列; C-C結合切断; C-Si結合生成; C-Si結合切断; カルボニルのシリルシアノ化; シリル配位子; 酸化的付加反応; シリル転位反応; メタラホスファシ

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

该项目的目的是创建具有13至16族元素配体的过渡金属配合物的新化学。该项目还涉及配位层中具有两种或多种典型元素的过渡金属配合物。 1.磷化物配合物的研究：制备了一些带有磷化物侧链环戊二烯基配体的Zr和Hf配合物，这些配合物被发现可用作乙烯聚合和聚合反应的催化剂。乙烯/苯乙烯与MMAO结合进行共聚。 2. 有机腈C-C键断裂：发现铁甲硅烷基络合物具有断裂有机腈C-C键的能力，理论计算提出了合理的断裂反应路径。建立了有机腈的C-C键，并提出了铁催化醛的甲硅烷基化反应机理。 3．和酮：醛或酮的甲硅烷基化是在含有催化量的铁甲基络合物存在下，通过 Et_3SiH 与 MeCN 光反应产生的 Et_3SiCN 的溶液中进行的。催化剂既可用于 MeCN 的 C-C 键断裂和伴随的 Si-C 键形成，也可用于 MeCN 中的 Si-C 键断裂4. 亚磷酸硼基配合物的研究：Mo甲基配合物在BH_3-P(OMe)(NMeCH_2)_2存在下发生光反应，生成亚磷酸硼基Mo配合物，该配合物与Mo-B和B-P反应。键断裂，其热反应导致B-H键断裂。5．亚磷酸锍配合物：具有两个或三个二氨基取代的亚磷酸酯的Mo配合物与TMSOTf反应得到相应的阳离子亚磷酸锍配合物。X射线结构分析和NMR谱显示优先非桥联结构已被纳入研究。亚磷酸鏻配合物的非桥联形式的优先选择，以及亚磷酸鏻盐配合物的优先选择类似的亚甲硅基烷氧基甲硅烷基络合物的桥接形式。

项目成果

Ethylene polymerization and ethylene/styrene copolymerization with secondary phosphine-pendant and phosphide-pendant complexes of Zr and Hf

• DOI: 10.1016/j.molcata.2004.06.024
• 发表时间: 2004-11
• 期刊: Journal of Molecular Catalysis A-chemical
• 作者: T. Ishiyama;K. Miyoshi;H. Nakazawa

Chloropyridinebis[tricarbonyl(η^5-cyclopentadienyl)tungstenio]indium

氯吡啶双[三羰基(η^5-环戊二烯基)钨]铟

• 发表时间: 2005
• 期刊: Acta Crystallographica E61
• 作者: H.Nakazawa;M.Itazaki;M.Owaribe
• 通讯作者: M.Owaribe

特許

专利

• 发表时间: 2008

H.Nakazawa: "C-C Bond Cleavage of Acetonitrile by a Carbonyl Iron Complex with a Silyl Ligand"Organometallics. 23・1. 117-126 (2004)

H.Nakazawa：“带有甲硅烷基配体的羰基铁络合物对乙腈的 C-C 键断裂”有机金属学 23・1（2004 年）。

Synthesis and Reactivity of a Phosphite-Boryl Complex of Molybdenum : Formation of (η^5-C_5Me_5)Mo(CO)_3(BH_2・phsphite) and its Mo-B, B-P, and B-H Bond Reactions

钼的亚磷酸硼基络合物的合成和反应性：(η^5-C_5Me_5)Mo(CO)_3(BH_2・亚磷酸盐)的形成及其Mo-B、B-P和B-H键反应

• 发表时间: 2006
• 期刊: Organometallics 25
• 作者: Takao;T.;Yoshida;S.;Suzuki;H.;H.Kusama;H.Nakazawa
• 通讯作者: H.Nakazawa