Synthesis of Base-Free Silyl (silylene) and Germyl (germylene) Complexes

无碱基甲硅烷基和甲锗烷基配合物的合成

• 批准号: 11640554
• 负责人: UENO Keiji
• 金额: $ 2.18万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640554/
• 关键词: Silylene Complexes; Germylene Complexes; Reactivity; Migration; Tungsten Complexes; Unsaturated Bonding; Isomerization; Isocarbonyl Complexes; ガリレン錯体; 1,3-転移; 動的挙動

1. Photolysis of Cp^*W(CO)_3Me (Cp^*=η-C_5Me_5) in the presence of excess HSiMe_2SiMe_3 afforded yellow crystals of a self-stabilized silyl (silylene) tungsten complex with a dimeric structure, [Cp^*W(CO)_2(=SiMe_2)(SiMe_3)]_2(1). In contrast, photolysis of Cp^*W(CO)_3Me in the presence of HSiMe_2SiMeMes_2 (Mes=2,4,6-Me_3C_6H_2) afforded a silyl (silylene) tungsten complex Cp^*W(CO)_2(=SiMes_2)(SiMe_3)(2). Complex 2 is the first "base-free" silyl (silylene) complex. X-ray crystal structure analysis of complex 1 and 2 revealed the significantly short W=Si bond compared to the W-Si bond. The ^<29> Si NMR signal of the silylene ligand for 2 appeared at remarkably low field (δ380.9 ppm) with a tungsten satellite having a large coupling constant (^1J_<SiW>=154.9 Hz). These results clearly demonstrate the double bond character of tungsten-silylene bonding.2. Photolysis of Cp^*W(CO)_3GeMe_2GeMe_3 resulted in the formation of a "base-free" germyl (germylene) tungsten complex Cp^*W(CO)_2(=GeMe_2)(GeMe_3)(3) quantitatively. Complex 3 is the first germylene complex having only small methyl groups on the germanium atoms. Reaction of complex 3 with Fe_2(CO)_9 resulted in the formation of a germylene-bridged dimetal complex Cp^*(OC)_3W(μ-GeMe_2)Fe(CO)_3GeMe_3 quantitatively.

1. 在过量 HSiMe_2SiMe_3 存在下，Cp^*W(CO)_3Me (Cp^*=η-C_5Me_5) 光解，得到具有二聚结构的自稳定硅基（亚硅基）钨络合物的黄色晶体，[Cp^* W(CO)_2(=SiMe_2)(SiMe_3)]_2(1) 相反，光解。 Cp^*W(CO)_3Me 在 HSiMe_2SiMes_2 (Mes=2,4,6-Me_3C_6H_2) 存在下提供硅基（亚硅基）钨络合物 Cp^*W(CO)_2(=SiMes_2)(SiMe_3)(2)配合物2是第一个“无碱”甲硅烷基（亚硅基）配合物的X射线晶体结构分析。配合物1和2显示出与W-Si键相比显着短的W=Si键。2的亚硅基配体的^ 29 Si NMR信号出现在具有钨卫星的异常低场(δ380.9ppm)。大的耦合常数（^1J_<SiW>=154.9 Hz）这些结果清楚地证明了钨-硅烯键合的双键特征。2． Cp^*W(CO)_3GeMe_2GeMe_3 定量地形成了“无碱基”甲锗烷基（germyl）钨络合物 Cp^*W(CO)_2(=GeMe_2)(GeMe_3)(3) 络合物 3。配合物 3 与 Fe_2(CO)_9 的反应导致形成了锗原子上仅具有小甲基的亚甲甲配合物。亚甲甲桥联二金属配合物Cp^*(OC)_3W(μ-GeMe_2)Fe(CO)_3GeMe_3的定量分析。

项目成果

Hideki Kobayashi, Keiji Ueno, and Hiroshi Ogino: "Formation of Acyliron Complexes CpFe (CO){P(OR')_3"Chem.Lett.. 1999. 119-120 (1999)

Hideki Kobayashi、Keiji Ueno 和 Hiroshi Ogino：“Acyliron 配合物 CpFe (CO){P(OR)_3 的形成”Chem.Lett.. 1999. 119-120 (1999)

Takeshi Yamaguchi: "Synthesis and Structures of Mesitylgallylene-Bridged Diiron Complexes [Cp'Fe(CO)]_2(μ-CO)(μ-GaMes)"Organometallics. 20・3. 501-507 (2001)

Takeshi Yamaguchi：“三甲苯基桥联二铁络合物的合成和结构[CpFe(CO)]_2(μ-CO)(μ-GaMes)”有机金属学20・3 (2001)。

Hideki Kobayashi: "Synthesis and structure of the cationic external donor-stabilized silyleneiron complex by hydride abstraction from a (hydrosilyl)iron complex"Chem. Lett.. 1999・3. 239-240 (1999)

小林秀树：“通过从（氢硅基）铁络合物中提取氢化物来合成和结构阳离子外部供体稳定的硅烯铁络合物”Chem.Lett. 1999・3。

Hideki Kobayashi: "Formation of acyliron complexes CpFe(CO){P(OR')_3}COR' by reaction of silyliron complexes CpFe(CO)_2SiR_2 with alkylphosphites P(OR')_3"Chem.Lett.. 1999・2. 119-120 (1999)

小林秀树：“通过甲硅烷基铁配合物 CpFe(CO)_2SiR_2 与烷基亚磷酸酯 P(OR)_3 反应形成酰基铁配合物 CpFe(CO){P(OR)_3}COR”Chem.Lett.. 1999・2。 119-120 (1999)

Keiji Ueno: "Synthesis, crystal structures, and fluctional behavior of donor-bridged bis(silylene)molybdenum and -chromium complexes"Organometallics. 18・14. 2694-2699 (1999)

Keiji Ueno：“供体桥联的双（亚硅基）钼和铬配合物的合成、晶体结构和波动行为”有机金属学 18・14（1999）。