Syntheses and Reactivity of Metal Cluster Complexes with Borylene as a Bridging Ligand

以硼烯为桥联配体的金属簇配合物的合成及反应活性

• 批准号: 06640716
• 负责人: SHIMOI Mamoru
• 金额: $ 1.34万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06640716/
• 关键词: borylene; borane; boryl; metal complex; metal clusters; ボリレン錯体; ボリル錯体; ボラン錯体

[Co_2 (CO)_8] reacted with B_2H_4・2PMe_3 to form a borylene complex [Co_7 (CO)_7 (BHPMe_3)] where borylene is stabilized by the phosphine. This is the first example of a borylene bridged dinuclear complex. B-H and B-B bond fission accompanied the reaction. This is in contrast to hitherto known coordination compounds of electron precise boranes such as BH_3・PMe_3 and B_2H_4・2PMe_3 in which B-H or B-P bonding are kept intact. Ultraviolet irradiation of methyl complexes, [CpWMe (CO)_3] and [CpFeMe (CO)_2] which are electron-rich with cylopentadienyl group in the presence of BH_3・PMe_3 liberated methane to form boryl complexes [CpW (BH_2PMe_3) (Co)_3] and [CpFe (BH_2PMe_2)], respectively. These reactions were accompanied by the B-H bond cleavage. Phtochemical reaction of [Cr (CO)_6] in the presence of BH_3・PMe_2CH_2PMe_2・BH_3 gave a five-membered diborane derivative by the dehydrogenation and B-B bond formation, which coordinated two chromium moieties through four Cr-H-B bonds to form [{Cr (CO)_4}_2 (BH_2BH_2PMe_2CH_2PMe_2)]. The structure was analyzed by the X-ray crystallography. This cluster can be regarded as a dimetalatetraborane derivatives. Reaction of [Cp^*RuCl]_4 with BH_3・PMe cleaved a strong B-P bond followed by the Cl atom transfer to give a chlorotrihidroborato complex. This complex is expected to be a versatile starting material for the formation of borylene complex because it has a reactive B-Cl bond.

[Co 2（CO）_8]与B_2H_4·2PMe_3反应，生成配体[Co_7（CO）_7（BHPMe_3）]。这是第一个硼桥双核配合物的例子。B-H和B-B键的断裂伴随着反应的进行。这与目前已知的BH_3·PMe_3和B_2H_4·2PMe_3等精确电子硼烷的B-H或B-P键保持完整的配合物形成了鲜明的对比。[CpWMe（CO）_3]和[CpFeMe（CO）_2]在BH_3·PMe_3的存在下，分别在紫外光照射下释放出甲烷，生成[CpW（BH_2PMe_3）（Co）_3]和[CpFe（BH_2PMe_2）]。这些反应伴随着B-H键的断裂。[Cr（CO）_6]在BH_3·PMe_2CH_2PMe_2·BH_3存在下发生光化学反应，通过脱氢和B-B键的形成，得到一个五元乙硼烷衍生物，它通过四个Cr-H-B键与两个铬原子配位，形成[{Cr（CO）_4}_2（BH_2BH_2PMe_2CH_2PMe_2）]。通过X射线晶体学分析了其结构。这种簇合物可以看作是一种二金属四硼烷衍生物。[Cp^*RuCl]_4与BH_3·PMe反应，发生强的B-P键断裂和Cl原子转移，生成三氢硼氯配合物。由于该配合物具有反应性B-Cl键，因此有望成为形成亚硼配合物的通用起始材料。

项目成果

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M.Watanabe、I.Motoyama、T.Takayama、M.Shimoi 和 H.Sano：“碘的分子结构 [1.1] 二茂铁基钌茂基 ^ BF_4^-盐”J.Organomet.Chem.496。

M. Shimoi: "Syntheses and Struvtures of Transition Metal Complexes of Lewis Base Adducts of Borane and Borylene" “Current Topics in the Chemistry of Boron ", ed. G. W. Kabalka, Royal Society of Chemistry. 293-296 (1994)

M. Shimoi：“硼烷和硼烯的路易斯碱加合物的过渡金属络合物的合成和结构”，“硼化学的当前主题”，G. W. Kabalka 编辑，英国皇家化学学会 293-296 (1994)。

Y. Kawano: "Functionalization of the μ-Silylene Lgandin Cp_2Fe_2(CO)_3(μ-SiH^tBu)" J. Am. Chem. Soc.116. 8575-8581 (1994)

Y. Kawano：“μ-Silicon Lgandin Cp_2Fe_2(CO)_3(μ-SiH^tBu) 的功能化”J. Am. 8575-8581 (1994)。

M.Watanabe, I.Motoyama, M.Shimoi, and T.Iwamoto: "Molecular Structure of Mixed-Valence 1,1'-Biruthenocene Derivative, Iodobiruthenocenium (II,IV) Tetrafluoroborate" Inorg.Chem.33. 2518-2521 (1994)

M.Watanabe、I.Motoyama、M.Shimoi 和 T.Iwamoto：“混合价 1,1-Biruthenocene 衍生物、Iodobiruthenocenium (II,IV) 四氟硼酸盐的分子结构”Inorg.Chem.33。