nido-[1,2-C5(CH3)5RuH]2B3H7 | 221313-34-4

• 英文名称: nido-[1,2-C5(CH3)5RuH]2B3H7
• 英文别名: nido-1,2-((pentamethylcyclopentadienyl)Ru)2B3H9；nido-1,2-(Cp*RuH)2B3H7
• CAS: 221313-34-4
• 化学式: C₂₀H₃₉B₃Ru₂
• 分子量: 514.103
• InChiKey: ZAAQBXIUWPHHGN-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  丙炔酸甲酯 、 nido-[1,2-C5(CH3)5RuH]2B3H7 以 正己烷 为溶剂， 以53%的产率得到[1,2-C5(CH3)5RuH]2CHC(CO2CH3)B2H4
  参考文献：
  名称：

  Reactivity of Dimetallapentaboranes—nido-[Cp$\rm{^{{\ast}}_{2}}$M2B3H7]—with Alkynes: Insertion to Form a Ruthenacarborane (M=RuH) versus Catalytic Cyclotrimerization to Form Arenes (M=Rh) This work was supported by the National Science Foundation. Cp*=η-C5Me5.

  摘要：

  DOI：

  10.1002/1521-3773(20011203)40:23<4498::aid-anie4498>3.0.co;2-3

文献信息

• Reactions of nido-1,2-(Cp*RuH)2B3H7 with RCCR′ (R, R′=H, Ph; Me, Me) to yield novel metallacarboranes
  作者：Hong Yan、Alicia M. Beatty、Thomas P. Fehlner

  DOI：10.1016/s0022-328x(03)00172-4

  日期：2003.8

  2-butyne, to nido-1,2-(Cp*RuH)2B3H7 (1) at ambient temperature produces nido-1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-C2B2H4 (2), nido-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B2H4 (3), and nido-1,2-(Cp*RuH)2-4-Et-4,5-C2B2H5 (4), in parallel paths. On heating, 2, which contains a novel exo-polyhedral borane ligand, is converted into closo-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B3H3 (5) and nido-1,6-(Cp*Ru)2-4,5-Me2-4,5-C2B2H6

  在环境温度下将内部炔烃2-丁炔加到nido -1,2-（CP * RuH）2 B 3 H 7（1）上可产生nido -1,2-（CP * Ru）2（μ-H ）（μ-BH 2）-4,5--ME 2 -4,5--C 2乙2 ħ 4（2），nido- 1,2-（CP *期RuH）2 -4,5--ME 2 -4 ，5-C 2 B 2 H 4（3）和nido- 1,2-（CP * RuH）2 -4-Et-4,5-C 2 B2 H 5（4），平行路径。在加热时，2，其中包含一个新的外型-polyhedral硼烷配位体，被转换成闭合碳-1,2-（CP *期RuH）2 -4,5--ME 2 -4,5--C 2乙3 ħ 3（5）和nido -1,6-（CP * Ru）2 -4,5-Me 2 -4,5-C 2 B 2 H 6（6）后者是3的骨架异构体。用2-丁炔加热2会生成Nido-1,2-（CP * RuH）2
• Insertion of B−X (X = Cl, SMe₂) Moieties into Ruthenaborane Frameworks:  Synthesis and Characterization of (η⁵-C₅Me₅Ru)₂(μ-H)B₄H<i>_m</i>Cl<i>_n</i>, (<i>m</i>, <i>n</i> = 4, 3; 5, 2; 7, 2), <i>c</i><i>loso</i>-1-(SMe₂)-2,3-(η⁵-C₅Me₅Ru)₂(μ₃-H)B₅HCl₃, and <i>c</i><i>loso</i>-2,3-(η⁵-C₅Me₅Ru)₂B₆H₃Cl₃
  作者：Sundargopal Ghosh、Thomas P. Fehlner、Alicia M. Beatty、Bruce C. Noll

  DOI：10.1021/om050083y

  日期：2005.5.1

  The reaction of nido-1,2-(eta(5)-C5Me5Ru)(2)(mu-H)(2)B3H7 (1) with the dichloroborane BHCl2 center dot SMe2 results in the formation of three sets of B-Cl inserted metallaborane products: nido-1,2(eta(5)-C5Me5Ru)(2)(mu-H)B4H7Cl2 (2), pileo-2,3-(eta(5)-C5Me5Ru)(2)(mu-H)B4H5Cl2 (three geometric isomers, 3-5), and pileo-2,3-(eta(5)-C5Me5Ru)(2)(mu-H)B4H4Cl3 (a pair of geometric isomers, 6 and 7). When the same reaction was carried out under more forcing conditions, three new metallaborane compounds, closo-1-(SMe2)-2,3-(eta(5)-C5Me5Ru)(2)(mu(3)-H)B5HCl3 (a pair of geometric isomers, 8 and 9) and closo-2,3-(eta(5)-C5Me5Ru)(2)B6H3Cl3 (10), were isolated in low yield in addition to 2-7. Compounds 8 and 9 exhibit a capped-octahedral geometry, and 10 exhibits a seven-sep (skeletal electron pair) bicapped-octahedral geometry. Reaction of nido-2,4-(eta(5)-C5Me5Ru)(2)B6H12 and nido-2,3-(eta(5)-C5Me5Ru)(2)B8H12 with BHCl2 center dot SMe2 results in substitution of terminal H by Cl, producing nido-2,4-(eta(5)-C5Me5Ru)(2)B6H10Cl2 (11) and nido-2,3-(eta(5)-C5Me5Ru)(2)B8H11Cl (12) in 82% and 75% yields, respectively.
• Cooperative Metal−Boron Interactions in the Reaction of <i>n</i><i>ido</i>-1,2-(Cp*RuH)₂B₃H₇, Cp* = η⁵-C₅Me₅, with HC⋮CPh
  作者：Hong Yan、Bruce C. Noll、Thomas P. Fehlner

  DOI：10.1021/ja042439n

  日期：2005.4.1

  Products of the reaction of nido-1,2-(Cp*RuH)(2)B3H7, 1, and phenylacetylene demonstrate the ways in which cluster metal and main group fragments can combine with an alkyne. Observed at 22 degrees C are (a) reduction to mu-alkylidene Ru-B bridges (isomers nido-1,2-(Cp*Ru)(2)(1,5-mu-CPh}Me)B3H7, 2, and nido-1,2-(Cp*Ru)(2)(1,5-mu-CCH2Ph}H)B3H7, 3), (b) reduction to exo-cluster alkyl substituents on boron (nido-1,2-(Cp*RuH)(2)-3-CH2CH2Ph-B3H6, 4), (c) cluster insertion with extrusion of a BH2 fragment into an exo-cluster bridge (nido-1,2-(Cp*Ru)(2)(mu-H)(mu-BH2)-4-or-5-Ph-4,5-C2B2H5, 5), (d) combined insertion with BH2 extrusion and reduction (nido-1,2-(Cp*Ru)(2)(mu-H)(mu-BH2)-3-CH2CH2Ph-5-Ph-4,5-C2B2H4, 6), (e) insertion and loss of borane with and without reduction (nido-1,2-(Cp*Ru)(2)-5-Ph-4,5-C2B2H7, and isomers nido-1,2-(Cp*Ru)(2)-3-CH2CH2Ph-4-(and-5-)Ph-C2B2H6, 8 and 9), and (f) insertion and borane loss plus reduction (nido-1,2-(Cp*Ru)(2)-3-(trans-CH=CHPh)-5-Ph-4,5-C2B2H6, 10). Along with 7, 8, and 10, the reaction at 90 C generates products of insertion and nido- to closo-cluster closure (closo-4-Ph-1,2-(Cp*RuH)(2)-4,6-C2B2H3, 11, closo-1,2-(Cp*RuH)(2)-3-CH2CH2Ph-5-Ph-7-CH2CH2Ph-4,5-C2B3H2, 12, closo-1,2-(Cp*RuH)(2)-5-Ph-4,5-C2B3H4, 13, and isomers c/oso-1,2-(Cp*RuH)(2)-3-and-7-CH2CH2Ph-5-Ph-4,5-C2B3H3, 14 and 15). The clusters with an exo-cluster bridging BH2 groups are shown to be intermediates by demonstrating that the major products 5 and 6 rearrange to 13 and convert to 14, respectively. 14 then isomerizes to 15, thus connecting low- and high-temperature products. Finally, all available information shows that the high reactivity of 1 with alkynes can be associated with the "extra" two Ru-H hydrides on the framework of 1 which are required to meet the nido-cluster electron count.