bis(η6-C6Me6) trihydridodiruthenium tetrafluoroborate | 681431-88-9

• 英文名称: bis(η6-C6Me6) trihydridodiruthenium tetrafluoroborate
• 英文别名: [(η6-C6Me6)2Ru2(μ-H)3][tetrafluroborate]；[(η6-C6Me6)2Ru2(μ2-H)3][BF4]；[(η6-C6Me6)2Ru2(μ2-H)3]BF4
• CAS: 681431-88-9
• 化学式: BF₄*C₂₄H₃₉Ru₂
• 分子量: 616.518
• InChiKey: SQZNBHRGKZBVLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis(η6-C6Me6) trihydridodiruthenium tetrafluoroborate 、 二-叔丁基膦 以 二氯甲烷 为溶剂， 以100%的产率得到[(η6-C6Me6)2Ru2(μ2-P(t-Bu)2)(μ2-H)2][BF4]
  参考文献：
  名称：

  Reactivity of the Unsaturated Complex [(C₆Me₆)₂Ru₂(μ₂-H)₃]⁺ toward Phosphines:  Synthesis and Molecular Structure of the Dinuclear Cations [(C₆Me₆)₂Ru₂(μ₂-PR₂)(μ₂-H)₂]⁺ and Characterization of the P−C Bond Activation Intermediate [(C₆Me₆)₂Ru₂(μ₂-PPh₂)(μ₂-H)(μ₂-Ph)]⁺

  摘要：

  The unsaturated trihydrido complex [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) reacts with diaryl- or dialkyl-phosphines PR2H to give the dinuclear cations [(C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) (R= Ph, 1; R = t-Bu, 2). Surprisingly, complexes of the type [(C6Me6)(2)Ru-2(mu(2)-PR2)(mu(2)-H)(2)](+) with R = Ph (1), n-Bu (3), n-Oct (4) are also accessible in high yield from the reaction of [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) with the corresponding triaryl- or trialkylphosphine PPh3, P(n-Bu)(3), or P(n-Oct)(3) by carbon-phosphorus bond cleavage. A possible intermediate of the reaction with PPh3, [(C6Me6)(2)Ru-2(mu(2)-PPh2)(mu(2)-H)(mu(2)-Ph)](+) (5), could be isolated from the reaction mixture as the tetrafluoroborate salt, the single-crystal X-ray structure analysis of which reveals a bridging phenyl ligand coordinated in an mu(1)-mu(2) fashion to the diruthenium backbone. With the mixed phosphine PMe2Ph, [(C6Me6)(2)Ru-2(mu(2)-H)(3)](+) reacts to give [(C6Me6)(2)Ru-2(mu(2)-PMe2)(mu(2)-H)(2)](+) (6) and the corresponding intermediate [(C6Me6)(2)Ru-2(mu(2)-PMe2)(mu(2)-H)(mu(2)-Ph)](+) (7). All dinuclear cations are isolated as the tetrafluoroborate salts.

  DOI：

  10.1021/om049025n
• 作为产物：
  描述：

  氟硼酸钠 、 [Ru(p-cymene)(H₂O)₃]SO₄ 、 [(η(6)-C6Me6)Ru(H2O)3][SO4] 、 sodium tetrahydroborate 以 水 为溶剂， 以32%的产率得到[(η6-C6Me6)(η6-p-iPrMeC6H4)Ru2(μ2-H)3][BF4]
  参考文献：
  名称：

  具有固有骨架手性的四面体Ru 3 O团簇的合成与表征：完整团簇催化概念的手性探针†

  摘要：

  为了提供证据支持或反对通过完整的含氧代帽的三核芳烃钌簇进行催化氢化的假说，已将具有三种不同芳烃配体的阳离子Ru 3 O簇（本征上为手性四面体）合成为外消旋混合物。通过在三个不同的芳烃配体之一处引入手性辅助取代基，可以分离两种非对映异构体。X射线晶体学，UV和IR区域的圆二色性以及NMR光谱中的手性位移试剂证明了手性Ru 3 O骨架。使用手性Ru 3催化前手性底物2-乙酰氨基丙烯酸甲酯的氢化反应O团簇未显示不对称诱导，表明催化活性物种不是完整的Ru 3 O团簇。

  DOI：

  10.1021/om050643t

文献信息

• Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes: Synthesis and Structure of Thiolato‐Bridged Diruthenium Cations of the Type [H ₂ (arene) ₂ Ru ₂ ( <i>p</i> ‐X−C ₆ H ₄ −S)] ⁺ and [H(arene) ₂ Ru ₂ ( <i>p</i> ‐X−C ₆ H ₄ −S) ₂ ] ⁺
  作者：Mathieu J.‐L. Tschan、Frédéric Chérioux、Bruno Therrien、Georg Süss‐Fink

  DOI：10.1002/ejic.200400015

  日期：2004.6

  The cationic complexes [HRu2(η6-arene)2μ2-(p-X−C6H4)−S}2]+ and [H2Ru2(η6-arene)2μ2-(p-X−C6H4)−S}]+ (arene = 1,2,4,5-Me4C6H2 or C6Me6; X = Br and Me) are accessible in good yields from p-X−C6H4−SH with [H3Ru2(1,2,4,5-Me4C6H2)2][BF4] and [H3Ru2(C6Me6)2][BF4], respectively. The dibromo derivative [HRu2(C6Me6)2(p-Br−C6H4−S)2]+ is found to undergo double Suzuki coupling reactions with 3-thiophene boronic

  阳离子配合物[HRu2(η6-芳烃)2μ2-(pX-C6H4)-S}2]+和[H2Ru2(η6-芳烃)2μ2-(pX- )-S}]+（芳烃= 1,2,4,5-Me4C6H2 或 C6Me6；X = Br 和 Me) 可以从 pX- -SH 和 [H3Ru2(1,2,4,5-Me4C6H2)2][BF4] 和 [分别为 H3Ru2(C6Me6)2][BF4]。发现二溴衍生物 [HRu2(C6Me6)2(p-Br− −S)2]+ 与 3-噻吩硼酸发生双 Suzuki 偶联反应，得到 [HRu2(C6Me6)2(p-C4H3S− −) S)2]+。这种二溴配合物是在共轭分子的主链中插入双核氢化有机金属实体的潜在前体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Dinuclear (Arene)ruthenium Complexes Containing a Chiral‐at‐Phosphorus Phosphanido Bridge
  作者：Mathieu J.‐L. Tschan、Georg Süss‐Fink、Frédéric Chérioux、Bruno Therrien

  DOI：10.1002/ejic.200601174

  日期：2007.7

  6 H 4 )Ru 2 (μ 2 -H) 3 ] + reacts with PPh 2 (CH 2 ) 3 Ph to give the phosphanido complex [(η 6 -C6Me6)(η 6 -p-iPMeC 6 H 4 )-Ru 2 μ 2 -PPh(CH 2 ) 3 Ph}(μ 2 -H) 2 ] + (1), which contains a stereo-genic phosphorus atom in the bridge, and benzene. Heating of 1 in bromobenzene gives the first chiral-at-phosphorus diruthenium complex [(η 6 -C6Me6)Ru 2 μ 2 -PPh(CH2)3-η 6 -Ph}(μ 2 -Br) 2 ] + (3) due to the

  不饱和二钌阳离子 [(η 6 -C 6 Me 6 )(η 6 -P-iPrMeC 6 H 4 )Ru 2 (μ 2 -H) 3 ] + 与 PPh 2 (CH 2 ) 3 Ph 反应生成膦基复合物 [(η 6 -C6Me6)(η 6 -p-iPMeC 6 H 4 )-Ru 2 μ 2 -PPh(CH 2 ) 3 Ph}(μ 2 -H) 2 ] + (1)，其中包含一个桥中的立体磷原子和苯。1 在溴苯中加热得到第一个手性磷二钌配合物 [(η 6 -C6Me6)Ru 2 μ 2 -PPh(CH2)3-η 6 -Ph}(μ 2 -Br) 2 ] + (3 ) 由于对伞花烃配体被悬臂上的苯基取代，氢桥被溴桥取代。[3][BF 4 ] 的单晶 X 射线结构分析揭示了晶体中对映异构体 (Rp)-3 和 (Sp)-3 的外消旋混合物。相似地，[(η 6 -C6Me6)(η 6 -p-iPrMeC 6
• A Surprising Reaction of Trimethylphosphane with the Unsaturated Diruthenium Complex [(η ⁶ ‐C ₆ Me ₆ ) ₂ Ru ₂ (μ ₂ ‐H) ₃ ] ⁺ : Synthesis and Molecular Structure of the Cations [(η ⁶ ‐C ₆ Me ₆ )Ru ₂ (PMe ₃ ) ₃ (μ ₂ ‐H) ₃ ] ⁺ and [(η ⁶ ‐C ₆ Me ₆ ) ₂ Ru ₂ (PMe ₃ ) ₂ (μ ₂ ‐H)(H) ₂ ] ⁺
  作者：Mathieu J.‐L. Tschan、Frédéric Chérioux、Bruno Therrien、Georg Süss‐Fink

  DOI：10.1002/ejic.200600926

  日期：2007.2

  the P–C bond in the reaction with [(η6-C6Me6)2Ru2(μ2-H)3]+ to give phosphido-bridged diruthenium cations of the type [(η6-C6Me6)2Ru2(μ2-PR2)(μ2-H)2]+, trimethylphosphane surprisingly yields the substitution product [(η6-C6Me6)Ru2(PMe3)3(μ2-H)3]+ (1), as well as the racemic intermediate [(η6-C6Me6)2Ru2(PMe3)2(μ2-H)(H)2]+ (2), in the form of the tetrafluoroborate salts. In complex 2, the hydrido ligands

  而芳香族或脂肪族膦在与 [(η6-C6Me6)2Ru2(μ2-H)3]+ 反应中发生 P-C 键断裂，得到 [(η6-C6Me6)2Ru2( μ2-PR2)(μ2-H)2]+，三甲基磷烷出人意料地产生取代产物 [(η6-C6Me6)Ru2(PMe3)3(μ2-H)3]+ (1)，以及外消旋中间体 [( η6-C6Me6)2Ru2(PMe3)2(μ2-H)(H)2]+ (2)，以四氟硼酸盐的形式存在。在配合物 2 中，氢化配体在溶液中是流动的，如变温 1H NMR 光谱所示。阳离子 1 与对溴苯硫酚反应生成复合物 [(η6-C6Me6)2Ru2(PMe3)3μ2-(p-Br-C6H4)-S}(μ2-H)2]+ (3)，分离为四氟硼酸盐。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Dinuclear hexamethylbenzene ruthenium cations containing η1:η2-2-(ferrocenyl)ethen-1-yl ligands: Synthesis, structure, electrochemistry
  作者：Mathieu J.-L. Tschan、Bruno Therrien、Jiří Ludvík、Petr Štěpnička、Georg Süss-Fink

  DOI：10.1016/j.jorganchem.2006.07.007

  日期：2006.10

  The cationic ferrocenyl-containing complexes [(eta(6)-C6Me6)(2)Ru-2(mu-eta(1):eta(2)-CH-CHFc)(2)(mu-H)](+) (3) and [(eta(6)-C6Me6)(2)Ru-2(mu-eta(1):eta 2-CH-CHFc)(mu-H)](+) (4) have been synthesised in ethanol from ethynylferrocene and the dinuclear precursors [(eta(6)-C6Me6)(2)Ru-2(mu-H)(3)](+) (1) and [(eta(6)-C6Me6)(2)Ru-2(mu-PPh2)(mu-H)(2)](+) (2) respectively, and isolated as tetrafluoroborate salts. The spectroscopic data of 3 and 4 as well as the single-crystal X-ray diffraction analysis of [4][BF4] show that the alkyne function of ethynylferrocene has been converted to a sigma/pi-ethenyl ligand by transfer of a bridging hydride from the diruthenium backbone onto the alpha-carbon of the triple bond in ethynylferrocene. The ferrocenyl-containing diruthenium compounds [3][BF4] and [4][BF4] as well as their parent compounds [1][BF4] and [2][BF4] have been studied by voltammetric techniques: Whereas 1 shows only an irreversible Ru(II)/Ru(III) oxidation, the phosphido-bridged derivative 2 displays two well-separated one-electron redox processes. In the case of 3 and 4, the ferrocenyl substituents give rise to additional reversible ferrocene/ferrocenium waves. (c) 2006 Elsevier B.V. All rights reserved.