A functional hydrogenase model: reversible interconversion of H2 and H2O by a hydroxo/sulfido-bridged dinuclear ruthenium-germanium complex.
A functional hydrogenase model: reversible interconversion of H2 and H2O by a hydroxo/sulfido-bridged dinuclear ruthenium-germanium complex.
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DOI：
10.1021/ja711325f
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发表时间：
2008-02
影响因子：
15
通讯作者：
Tsuyoshi Matsumoto;Yukiko Nakaya;N. Itakura;K. Tatsumi
中科院分区：
文献类型：
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作者：
Tsuyoshi Matsumoto;Yukiko Nakaya;N. Itakura;K. Tatsumi
S/OH桥接双核Ru−Ge络合物阳离子[Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PR3)](BArF4) (3)，通过Dmp(Dep)Ge(μ-S)(μ-O)Ru(PR3) (1)与H(OEt2)2BArF4 (ArF = 3,5-(CF3)2C6H3) 被发现可在温和条件下促进轻松且可逆的 H2 活化，生成 H2O 和 [Dmp(Dep)Ge(μ-S)(μ-H)Ru(PR3)](BArF4) (4)。 4的μ-氢化物表现出质子行为，并且μ-氢化物的酸性足够高，足以将1转变为3。因此，当1的C6D6溶液与催化量的H(OEt2)2BArF4 (1 mol %)在H2气氛下加热至70°C并保持24小时时，[Dmp(Dep)Ge(μ-S)Ru(PR3)] (5)和H2O成立了。通过X射线分析确定了4和5的分子结构。在1到5的催化转化中，H2形式上被消耗为两个质子生成H2O，以及两个电子以Ge−Ru键或Ru d电子的形式存储在5中。使用 Ge−Ru 复合物激活 H2 提供了一个有趣的氢化酶功能模型，...
The S/OH bridged dinuclear Ru−Ge complex cation, [Dmp(Dep)Ge(μ-S)(μ-OH)Ru(PR3)](BArF4) (3), which was synthesized quantitatively by the protonation of Dmp(Dep)Ge(μ-S)(μ-O)Ru(PR3) (1) with H(OEt2)2BArF4 (ArF = 3,5-(CF3)2C6H3), was found to promote facile and reversible H2 activation leading to H2O and [Dmp(Dep)Ge(μ-S)(μ-H)Ru(PR3)](BArF4) (4) under mild conditions. The μ-hydride of 4 exhibits protonic behavior, and the acidity of the μ-hydride is sufficiently high to transform 1 into 3. Thus, when a C6D6 solution of 1 with a catalytic amount of H(OEt2)2BArF4 (1 mol %) was heated to 70 °C for 24 h under an H2 atmosphere, [Dmp(Dep)Ge(μ-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, H2 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 H2 using the Ge−Ru complexes provides an intriguing functional model of hydrogenases,...