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Study on Syntheses of Cationic Borane a Complexes and Heterolytic Cleavage of a Boron-Hydrogen Bond

阳离子硼烷配合物的合成及硼氢键杂解断裂的研究

基本信息

批准号：
15350031
负责人：
KAWANO Yasuro
金额：
$ 9.66万
依托单位：
The University of Tokyo
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

项目摘要

New borane complexes were synthesized by the coordination of borane-Lewis base adducts, which have extremely low p-accepting ability, to positively charged metal centers. In the complexes obtained, the bonding between the central metal and coordinated BH hydrogen atom has proved to be more stable than in the neutral borane complexes. Furthermore, it was found that the borane ligand was polarized through the coordination to the cationic center and thereby chemically activated.Cationic manganese and molybdenum borane complexes, [Mn(CO)_4(PR_3)(η^1-BH_3・PMe_3)]^+ (1) and [Cp^*Mo(CO)_3(η^1-BH_3・PMe_3)]^+ (2), were obtained by protonation of the corresponding boryl complexes. A ruthenium derivative, [CpRu(PMe_3_)2(η^1-BH_3・PMe_3)]^+(3), was prepared by the borane coordination to the coordinatively unsaturated species generated by the chloride abstruction of [CpRu(PMe_3)_2Cl].Compounds 1 and 2 decompose at room temperature through BH cleavage leaving a hydride onto the metal center, rather than through borane dissociation. This is a novel type of reaction, in which a BH bond is heterolytically activated on metal.It was difficult to isolate compounds 1 and 2 because their BH heterolytic cleavage rapidly proceeds. In contrast, by the use of the cationic yet inherently electron-rich metal fragment, the ruthenium complex 3 has been very stable that it has not undergone the BH cleavage under vacuum. This is probably due to the metal-borane linkage stabilized by the positive charge on the metal atom and modest polarization of the borane ligand caused by the electron-rich nature of the metal fragment. However, the presence of trace water promoted the BH heterolytic cleavage of 3.

硼烷-路易斯碱加合物具有极低的p接受能力，与带正电的金属中心配位，合成了新的硼烷配合物。在所得到的配合物中，中心金属与配位BH氢原子之间的键比中性硼烷配合物更稳定。此外，硼烷配体通过配位到阳离子中心而发生极化，从而被化学活化。通过相应的硼基配合物质子化反应得到了锰钼硼烷阳离子配合物[Mn(CO)_4(PR_3)(η^1- bh_3·PMe_3)]^+(1)和[Cp^*Mo(CO)_3(η^1- bh_3·PMe_3)]^+(2)。以[CpRu(PMe_3)_2Cl]的氯原子构筑生成的配位不饱和基团为配位，制备了钌衍生物[CpRu(PMe_3_)2(η^1-BH_3·PMe_3)]^+(3)。化合物1和2在室温下通过BH解理分解，在金属中心留下氢化物，而不是通过硼烷解离。这是一种新型的反应，在这种反应中，一个BH键在金属上被异聚激活。由于化合物1和2的BH异裂裂解速度快，分离难度大。相反，通过使用阳离子但本身富含电子的金属碎片，钌配合物3非常稳定，在真空下没有发生BH解理。这可能是由于金属原子上的正电荷稳定了金属-硼烷键，并且由于金属碎片的富电子性质导致硼烷配体的适度极化。然而，微量水的存在促进了3的BH异裂。

项目成果

期刊论文数量（20）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

A Computational Study on Fluxional Behavior of Group 6 and 7 Transition Metal Complexes of Borane-Lewis Base Adducts

硼烷-路易斯碱加合物第6族和第7族过渡金属配合物流动行为的计算研究

DOI：
发表时间：
2006
期刊：
Chem. Lett. 35
影响因子：
0
作者：
Yasuro Kawano;Taeko Kakizawa;Kazunori Yamaguchi;Mamoru Shimoi
通讯作者：
Mamoru Shimoi

Boryl Complexes and Cationic Borane a Complexes of Manganese : Heterolytic Cleavage of the Metal- coordinated BH a Bond

锰的硼基配合物和阳离子硼烷 a 配合物：金属配位 BH a 键的杂解断裂

DOI：
发表时间：
2004
期刊：
Boron Chemistry at the Beginning of the 21th Century, Scientific Publishers URSS
影响因子：
0
作者：
Yasuro Kawano;Takahiro Yasue;Mamoru Shimoi
通讯作者：
Mamoru Shimoi

Y.Kawano, T.Yasue, M.shimoi: "Boryl Complexes and Cationic Borane σComplexes of Manganese : Heterolytic Cleavage of the Metal-coordinated BH σBond"Boron Chemistry at the Beginning of the 21th Century. 234-238 (2003)

Y.Kawano、T.Yasue、M.shimoi：“锰的硼基络合物和阳离子硼烷 σ 络合物：金属配位 BH σ 键的杂解裂解”21 世纪初的硼化学 (2003)。