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

本项目的目的是创造具有13至16族元素配体的过渡金属络合物的新化学。在配位圈中含有两种或两种以上典型元素的过渡金属络合物也参与了这一项目。所获得的结果如下所示。磷化物配合物的研究：合成了一些含磷化物的环戊二烯配体的锆氢配合物。通过与MMAO的结合，发现这些络合物可以作为乙烯聚合和乙烯/苯乙烯共聚的催化剂。有机腈的C-C键断裂：发现一种硅铁络合物具有裂解有机腈的C-C键的能力。理论计算给出了合理的反应路径。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氰化：在VO…溶液中执行醛或酮的硅氰化在催化量的甲基铁络合物存在下，Et_3SiH与MeCN的光反应生成更多的Et_3SiCN。从起始铁络合物衍生出的一些铁络合物既是MeCN的C-C键断裂和伴随的Si-C键形成的催化剂，也是硅氰化反应中Si-C键断裂的催化剂。亚磷酸基硼络合物的研究：在BH_3-P(OMe)(NMeCH_2)_2存在下，钼甲基络合物与光反应生成亚磷酸基硼钼络合物。该络合物分别与MeI和PMe_3发生Mo-B键和B-P键的断裂反应，其热反应导致B-H键断裂。亚磷酸亚膦配合物的研究：与两个或三个二氨基取代亚磷酸盐的钼配合物与TMSOTf反应生成相应的阳离子亚磷酸亚膦配合物。X-射线结构分析和核磁共振谱表明该化合物具有择优的非桥联结构。用密度泛函理论计算研究了亚磷酸亚膦络合物的非桥联形式的偏好，以及类似的硅亚甲基烷氧基硅基配合物的桥联形式的偏好。较少

项目成果

Carbonyl(η5-cyclo­penta­dienyl)(tri­methyl­silyl isocyanide)(tri­phenyl­phosphine)­iron(II) tri­fluoro­methane­sulfonate di­chloro­methane hemisolvate

羰基(η5-环戊二烯基)(三甲基甲硅烷基异氰)(三苯基膦)三氟甲磺酸铁(II)二氯甲烷半溶剂化物

• DOI: 10.1107/s1600536805015308
• 发表时间: 2005
• 期刊: Acta Crystallographica Section E: Crystallographic Communications
• 作者: H. Nakazawa;Masumi Itazaki;Mari Owaribe
• 通讯作者: Mari Owaribe

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

Dicarbonyl(η^5-pentamethylcyclopentadienyl)(triphenylphosphine)iron(II)hexafluorophosphate

二羰基(η^5-五甲基环戊二烯基)(三苯基膦)六氟磷酸铁(II)

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

Iron-Complex-Catalyzed C-C Bond Cleavage of Organonitriles : Catalytic Catalytic Metathesis Reaction between H-Si and R-CN Bonds to Afford R-H and Si-CN Bonds

铁络合物催化有机腈的 C-C 键断裂：H-Si 和 R-CN 键之间的催化复分解反应以产生 R-H 和 Si-CN 键

• 发表时间: 2007
• 期刊: Chemistry - an Asian Journal (In press)
• 作者: N.Matubayasi;M.Nakahara;林久史;H.Nakazawa
• 通讯作者: H.Nakazawa