Establishment of syntheses of metal-rich metallaborane clusters using borane-Lewis base adducts

利用硼烷-路易斯碱加合物合成富金属金属硼烷簇的建立

• 批准号: 11440193
• 负责人: SHIMOI Mamoru
• 金额: $ 8.9万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11440193/
• 关键词: metallaboranes; ruthenaboranes; clusters; ruthenium; phosphines; arene ligand; クラスター化合物; アレーンルテナボラン; ルテナボチン

The purpose of this project was to establish new methods for the syntheses of metallaboranes with large M/B ratios using activation of borane-Lewis base adducts by transition metal complexes which we have developed recently. Reactions of organometallic ruthenium complexes with BH_3-THF gave cluster compounds with the Ru_2B_3, RU_2B_4, RuB_4 frameworks, and further reactions of these clusters with phosphines gave RU_2B_2, RuB_3 clusters with larger M/B ratios.The reaction of BH_3-THF with [Cp^*RuCl]_4 gave nido-[(Cp^*Ru(μ-H)}_2B_3H_7] (1), and 1 further reacted with BH_3-THF to give nido-[(Cp^*Ru(μ-H)}_2B_4H_9] (2). Reaction of 1 with phosphine derivatives underwent degradation and rearrangement of cluster frameworks, and the reaction modes depended on the nature of phosphines. In the reactions with PHPh_2 or P(OPh)_3 1 gave arachno-[(Cp^*_2Ru_2PR_3)(μ-H)_2B_3H_7] (3) adding phosphine to the basal metal. Reaction with P(OR)_3 underwent dehydrogenation rearragement to give nido-[(Cp^*_2Ru_2(μ-P(OR)_2}(μ-H)_2B_3H_5(OR)] (4). Reactions with PR_3, stronger bases gave [(Cp^*Ru)_2(μ-H)(PR_3)B_2H_5] (5) with elimination of BH_3-PR_3. Reaction using phenyl phosphines provided [(Cp^*Ru)_2(μ-PR_2)(B_2H_2)] (6) accompanied with benzene elimination and rearagement of the framework. NMR measurement showed the fraxional property of the cluster flamework of 6. Reaction of 5 with excess PR_3, underwent total degradation of the cluster to form mononuclear compounds, although 6 did not show any such reaction.Reaction of BH_3-THF and [(C_6Me_6)RuCl_2]_2 with a bulky ligand, C_6Me_6, afforded arachno-[(C_6Me_6)RuB_4H_<10>] (7) which contained only one metal fragment. Reaction of 7 with PMe_3 arachno-[(C_6Me_6)Ru(PMe_3)(B_3H_7)] (8) accompanied with the elimination of BH_3-PMe_3. This also shows that the reaction of the cluster with phosphine provides a route to the change of the M/B ratio.

本项目的目的是建立利用我们最近开发的过渡金属络合物活化硼烷-路易斯碱加合物来合成大M/B比金属硼烷的新方法。有机金属Ru与BH_3-四氢呋喃反应生成具有Ru_2B_3、Ru_2B_4、RuB_4骨架的簇合物，再与膦反应生成M/B比较大的Ru_2B_2、RuB_3簇合物。BH_3-四氢呋喃与[Cp^*Ru(μ-H)]_4反应得到NIDO-[(Cp^*Ru(Ru-H)}_2B_3H_7](1)，和1进一步与BH_3-四氢呋喃反应得到NIDO-[(Cp^*Ru(μ-H)}_2B_4H_9](2)。1与膦类化合物的反应经历了簇状骨架的降解和重排，反应方式取决于膦的性质。在与PhPh_2或P(OPh)_3的反应中，1得到了花生-[(Cp^*_2Ru_2PR_3)(μ-H)_2B_3H_7](3)。与P(OR)_3反应，经脱氢重排得到nido-[(Cp^*_2Ru_2(μ-P(OR)_2}(μ-H)_2B_3H_5(OR)](4)。与PR_3反应得到[(Cp^*Ru)_2(μ-H)(PR_3)B_2H_5](5)，消除了BH_3-PR_3。用苯膦反应得到[(Cp^*Ru)_2(μ-PR_2)(B_2H_2)](6)。5与过量的PR_3反应生成单核化合物，但6没有发生这种反应。BH_3-THF和[(C_6Me_6)RuCl_2]_2与大分子配体C_6Me_6反应，得到只含有一个金属碎片的花生-[(C_6Me_6)RUB_4H&lt；10&GT；](7)。7与PMe_3-[(C_6Me_6)Ru(PMe_3)(B_3H_7)](8)的反应伴随着BH_3-PMe_3的消除。这也表明簇合物与膦的反应为M/B比的变化提供了途径。

项目成果

L.N.Pangan, Y.Kawano, M.Shimoi: "Synthesis of nido-[1-OMe-2.3-(Cp^*Ru)_2{μ-P(OMe)_2}B_3H_5]Methoxy Transfer from Phosphorus to Boron and Cluster Core Rearrangement"Inorg. Chem.. 40. 1985-1986 (2001)

L.N.Pangan、Y.Kawano、M.Shimoi：“nido-[1-OMe-2.3-(Cp^*Ru)_2{μ-P(OMe)_2}B_3H_5]甲氧基从磷转移到硼和团簇核心的合成重排》Inorg. Chem. 40. 1985-1986 (2001)

Y.Kawano, H.Kawakami, M.Shimoi: "Synthesis, Structure, and Phosphine-Induced Degradation of Ruthenapentaborane Cluster with Sterically Demanding Hexamethyl benzene Ligan"Chem. Lett.. 1006-1007 (2001)

Y.Kawano、H.Kawakami、M.Shimoi：“具有空间要求的六甲基苯配体的钌五硼烷簇的合成、结构和膦诱导的降解”Chem。

Y.Kawano: "Synthesis, Structure, and Phosphine-Induced Degradation of a Ruthenapentaborane Cluster with a Sterically Damanding Haxamethylbenzene Ligard"Chem. Lett.. 1006-1007 (2001)

Y.Kawano：“具有空间破坏的六甲基苯配体的钌五硼烷簇的合成、结构和膦诱导降解”Chem。

Y. Kawano, H. Matsumoto, and M. Shimoi: "Synthesis of Diruthenaborane Clusters, [{(Cp^*Ru(μ-H)}_2B_3H_7], [{(Cp^*Ru)_2(μ-H)B_4H_9], and [(Cp^*Ru)_2(μ-H)(PMe_3)(μ-η^4-B_2H_5)]"Chem. Lett.. 489-490 (1999)

Y. Kawano、H. Matsumoto 和 M. Shimoi：“Diruthenaborane 簇的合成，[{(Cp^*Ru(μ-H)}_2B_3H_7]、[{(Cp^*Ru)_2(μ-H)B_4H_9” ]，和[(Cp^*Ru)_2(μ-H)(PMe_3)(μ-η^4-B_2H_5)]“化学快报.. 489-490 (1999)

Y.Kawano: "Synthesis of Diruthenaborane Clusters, [{Cp^*Ru(μ-H)}_2B_3H_7],[{(Cp^*Ru)_2(μ-H)B_4H_9], and [(Cp^*Ru)_2(μ-H)(PMe_3)(μ-η^4-B_2H_5)]"Chem. Lett.. 489-490 (1999)

Y.Kawano：“Diruthenaborane 簇的合成，[{Cp^*Ru(μ-H)}_2B_3H_7]、[{(Cp^*Ru)_2(μ-H)B_4H_9] 和 [(Cp^*Ru) _2(μ-H)(PMe_3)(μ-η^4-B_2H_5)]《化学快报》489-490 (1999)