Study on the transition metal complexes with unstable silicon and germanium ligands

不稳定硅、锗配体过渡金属配合物的研究

• 批准号: 15350030
• 负责人: UENO Kenji
• 金额: $ 7.1万
• 依托单位: GUNMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350030/
• 关键词: Unsaturated bonding; Silicon; Transition metal complexes; Germanium; Silylene; Germylene; Reactivity; Structure; シリレン錯体; シリル(シリレン)錯体; タングステン錯体; モリブデン錯体; 哲錯体; シリリン錯体; 多核錯体; シロキシ錯体; 鉄錯体; 転位反応; タングステン; モリブデン; 鉄; ジシラン

(1) Silyl(silylene)tungsten and -molybdenum complexes Cp^*M(CO)_2(=SiMes_2)(SiMe_2) (M = Mo, W ; Mes = mesityl) have been synthesized photochemically. Reaction of the molybdenum complex with N,N-dimethylpyridine (DMAP) and nitriles afforded Cp^*Mo(CO)_2(=SiMesMe・DMAP(SiMesMe_2) and Cp^*M(CO)_2(RC=NSiMe_2SiMes_2Me_2), respectively. In contrast to the molybdenum complex, the tungsten complex did not react with DMAP and nitriles under the same reaction conditions. Reaction of the tungsten and molybdenum complexes with isocyanides gave Cp^*M(CO)_2(=Si(Mes)(C(Mes)=NR))(SiMesMe_2).(2) A germyl(germylene)tungsten complex has been synthesized in a good yield. Reaction of the germyl(germylene) complex with Fe(CO)_5 resulted in the migration of germyl group from tungsten to iron atom to form a germylene-bridged iron-tungsten complex.(3) Photo irradiation of a iron complex in the presence of dihydrogerman Mes_2GeH_2 afforded a novel germylene-bridged diiron complex with a triplet ground state.(4) The first silylene complex of early transition metal has been synthesized using methoxydisilane and tantalum complex in a moderate yield. The complex was characterized by crystal structure analysis.

(1) 光化学合成了硅基(亚硅基)钨和硅基钼配合物Cp^*M(CO)_2(=SiMes_2)(SiMe_2) (M = Mo, W ; Mes = 基)。钼络合物与N,N-二甲基吡啶(DMAP)和腈反应，分别得到Cp^*Mo(CO)_2(=SiMesMe·DMAP(SiMesMe_2)和Cp^*M(CO)_2(RC=NSiMe_2SiMes_2Me_2)。与钼络合物相反，钨络合物不发生反应 在相同的反应条件下，用DMAP和腈进行反应。钨钼配合物与异氰化物反应得到Cp^*M(CO)_2(=Si(Mes)(C(Mes)=NR))(SiMesMe_2)。(2)以良好的收率合成了甲锗烷基(germyl)钨配合物。甲锗烷基（甲锗烷基）络合物与 Fe(CO)_5导致甲硼基从钨迁移到铁原子上，形成亚甲甲桥联铁钨配合物。(3)在二氢锗Mes_2GeH_2存在下对铁配合物进行光照射，得到了具有三线态基态的新型亚甲甲桥联二铁配合物。(4)第一个早期过渡金属硅撑配合物已被合成 甲氧基乙硅烷和钽络合物的产率适中。通过晶体结构分析对该配合物进行了表征。

项目成果

Synthesis, Structure, and Reactivity of Cationic Base-Stabilized Gallyleneiron Complexes

阳离子碱稳定的没食子铁配合物的合成、结构和反应活性

• 发表时间: 2003
• 期刊: Appl. Organometal. Chem. 17
• 作者: Bahaa A.S.Mohamed;Mami Kikuchi;Hisako Hashimoto;Keiji Ueno;Hiromi Tobita;Hiroshi Ogino;Keiji Ueno
• 通讯作者: Keiji Ueno

Synthesis and Structure of a Base-Stabilized Silyl(silylene)tantalum, Complex

碱稳定的硅基（亚硅基）钽配合物的合成和结构

• 发表时间: 2005
• 期刊: Chem.Lett. 34
• 作者: Hidenori Koshikawa;Masaaki Okazaki Shun-ichi Matsumoto;Keiji Ueno;Hiromi Tobita. Hiroshi Ogino
• 通讯作者: Hiromi Tobita. Hiroshi Ogino

Keiji Ueno, Takahito Watanabe, Hiroshi Ogino: "Synthesis, Structure, and Reactivity of Cationic Base-Stabilized Gallyleneiron Complexes"Appl.Organometal.Chem.. 17. 403-408 (2003)

Keiji Ueno、Takahito Watanabe、Hiroshi Ogino：“阳离子碱稳定的没食子铁络合物的合成、结构和反应性”Appl.Organometal.Chem.. 17. 403-408 (2003)

Synthesis and Characterization of Triplet Germylene-Bridged Diiron Complexes and Singlet Stannylene-Bridged Diiron complexes

三重态甲锗烷桥联铁配合物和单线态亚锡桥联铁配合物的合成与表征

• 发表时间: 2004
• 期刊: Chem.Lett. 33
• 作者: Bahaa A.S.Mohamed;Mami Kikuchi;Hisako Hashimoto;Keiji Ueno;Hiromi Tobita;Hiroshi Ogino
• 通讯作者: Hiroshi Ogino

Synthesis and Structures of the First Titanium(IV) Complexes with Cyclic Tetrasiloxide Ligands : Incomplete and Complete Cage Titanosiloxanes

第一个具有环状四硅氧化物配体的钛（IV）配合物的合成和结构：不完全和完全笼状钛硅氧烷

• 发表时间: 2005
• 期刊: Chem Lett. 34
• 作者: Masakazu Hirotsu;Shinsuke Taruno;Takashi Yoshimura;Keiji Ueno;Masafumi Unno;Hideyuki Matsumoto
• 通讯作者: Hideyuki Matsumoto