[(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-OH)Ru(PPh3)](B(3,5-(CF3)2C6H3)4) | 912672-52-7

• 英文名称: [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-OH)Ru(PPh3)](B(3,5-(CF3)2C6H3)4)
• 英文别名: [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-OH)Ru(PPh3)][B(C6H3(CF3)2-3,5)4]；[(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(.mu-OH)RuPPh3]B(3,5-(CF3)2C6H3)4
• CAS: 912672-52-7
• 化学式: C₃₂H₁₂BF₂₄*C₅₂H₅₄GeOPRuS
• 分子量: 1794.92
• InChiKey: VERKGYYOCWYEON-PQCNTCQQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 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：

  [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-OH)Ru(PPh3)](B(3,5-(CF3)2C6H3)4) 、 四乙基氯化铵 以 四氢呋喃 为溶剂， 以99%的产率得到[(2,6-dimesitylphenyl)(2,6-diethylphenyl)(OH)Ge(μ-S)RuCl(PPh3)]
  参考文献：
  名称：

  Synthesis of Oxo- and Sulfido-Bridged Germanium−Ruthenium Complexes and Reactions on the Chalcogenido Bridges

  摘要：

  A series of heterodinuclear germanium-ruthenium complexes having sulfido/oxo bridges, Dmp(Dep)Ge(mu-E-1)(mu-E-2)Ru(eta(6)-arene) (E-1, E-2 = S, O; arene) benzene, p-cymene; Dmp = 2,6-dimesitylphenyl, Dep) 2,6-diethylphenyl) were synthesized by the reaction of [Ru(eta(6)-arene)Cl-2](2) and the corresponding diarylgermanedichalcogenoles, Dmp(Dep)Ge((EH)-H-1)((EH)-H-2). The reaction with tertiary phosphines gave the corresponding adducts Dmp(Dep)Ge(mu-S)(mu-E)Ru(PR3) (E = S, O; R = Ph, Et), in which the arene ligand on the ruthenium was replaced by a mesityl group of Dmp. When Dmp(Dep)Ge(mu-S)(2)Ru(PPh3) was treated with the Bronsted acids H(OEt2)(2)BAr4F and HOTf, a sulfido bridge was protonated to afford [Dmp(Dep)Ge(mu-S)(mu-SH)Ru(PPh3)]X (X = BAr4F, OTf). Likewise, the methylation reaction with Me3OBF4 proceeded at a mu-S, generating [Dmp(Dep)Ge(mu-S)(mu-SMe)Ru(PPh3)](BF4). On the other hand, protonation of Dmp(Dep)Ge(mu-S)(mu-O)Ru(PPh3) gave a mu-OH complex, [Dmp(Dep)Ge(mu-S)(mu-OH)Ru(PPh3)](+), while the analogous methylation afforded the cationic mu-SMe complex [Dmp(Dep)Ge(mu-SMe)(mu-O)Ru(PPh3)](+).

  DOI：

  10.1021/om060449m
• 作为产物：
  描述：

  [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-SH)Ru(PPh3)][B(C6H3(CF3)2-3,5)4] 、 水 以 氘代四氢呋喃 为溶剂， 生成 [(2,6-dimesitylphenyl)(2,6-diethylphenyl)Ge(μ-S)(μ-OH)Ru(PPh3)](B(3,5-(CF3)2C6H3)4)
  参考文献：
  名称：

  硫化物桥联的双核Ru / Ge络合物的二氢活化作用：洞悉[NiFe]氢化酶未就绪状态。

  摘要：

  AS / SH桥接异核Ru / Ge络合物阳离子与H（2）反应，提供mu-S / mu-H络合物。与mu-S / mu-OH配合物相比，反应明显慢。因此，mu-S / mu-SH和mu-S / mu-OH复合物可能分别为[NiFe]氢化酶的未就绪和就绪状态提供模型。

  DOI：

  10.1039/c0cc03391j

文献信息

• A Functional Hydrogenase Model:  Reversible Interconversion of H₂ and H₂O by a Hydroxo/Sulfido-Bridged Dinuclear Ruthenium−Germanium Complex
  作者：Tsuyoshi Matsumoto、Yukiko Nakaya、Naohisa Itakura、Kazuyuki Tatsumi

  DOI：10.1021/ja711325f

  日期：2008.2.1

  The S/OH bridged dinuclear Ru-Ge complex cation, [Dmp(Dep)Ge(mu-S)(mu-OH)Ru(PR3)](BAr4F) (3), which was synthesized quantitatively by the protonation of Dmp(Dep)Ge(mu-S)(mu-O)Ru(PR3) (1) with H(OEt2)(2)BAr4F (Ar-F = 3,5-(CF3)(2)C6H3), was found to promote facile and reversible H-2 activation leading to H2O and [Dmp(Dep)Ge(mu-S) (mu-H)Ru(PR3)](BAr4F) (4) under mild conditions. The mu-hydride of 4 exhibits protonic behavior, and the acidity of the mu-hydride is sufficiently high to transform 1 into 3. Thus, when a C6D6 solution of 1 with a catalytic amount of H(OEt2)(2)BAr4F (1 mol %) was heated to 70 degrees C for 24 h under an H-2 atmosphere, [DmP(Dep)Ge(mu-S)Ru(PR3)] (5) and H2O were formed. The molecular structures of 4 and 5 were determined by X-ray analysis. In the catalytic conversion of 1 to 5, H-2 is consumed formally as two protons generating H2O, and two electrons which are stored in 5 as the Ge-Ru bond or as Ru d-electrons. Activation of H-2 using the Ge-Ru complexes provides an intriguing functional model of hydrogenases, where the mu-O complex 1, the mu-OH complex 3, and the mu-H complex 4 may respectively correspond to the Ni-SU, the Ni-Sl(r), and the Ni-Sl(a) states of [NiFe] hydrogenase.