Protonation Equilibrium and Hydrogen Production by a Dinuclear Cobalt–Hydride Complex Reduced by Cobaltocene with Trifluoroacetic Acid,Journal of the American Chemical Society

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Protonation Equilibrium and Hydrogen Production by a Dinuclear Cobalt–Hydride Complex Reduced by Cobaltocene with Trifluoroacetic Acid
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2013-10-01 , DOI: 10.1021/ja408080z
Sukanta Mandal ₁ , Shinya Shikano ₂ , Yusuke Yamada ₂ , Yong-Min Lee ₁ , Wonwoo Nam ₁ , Antoni Llobet _{1,

3} , Shunichi Fukuzumi _{1,

2}

Affiliation

A dinuclear Co complex with bis(pyridyl)pyrazolato (bpp(-)) and terpyridine (trpy) ligands, [Co(III)2(trpy)2(μ-bpp)(OH)(OH2)](4+) (1(4+)), undergoes three-electron reduction by cobaltocene in acetonitrile to produce 1(+), which is in the protonation equilibrium with the Co(II)Co(III)-hydride complex, and the further protonation of the hydride by trifluoroacetic acid yields hydrogen quantitatively. The kinetic study together with the detection of the Co(II)Co(III)-hydride complex revealed the mechanism of the hydrogen production by the reaction of 1(+) with trifluoroacetic acid.

中文翻译：

由二茂钴和三氟乙酸还原的双核钴-氢化物配合物的质子化平衡和产氢

具有双(吡啶基)吡唑啉根 (bpp(-)) 和三联吡啶 (trpy) 配体的双核 Co 复合物，[Co(III)2(trpy)2(μ-bpp)(OH)(OH2)](4+) ( 1(4+))，在乙腈中被二茂钴进行三电子还原，生成 1(+)，与 Co(II)Co(III)-氢化物配合物处于质子化平衡，氢化物进一步质子化通过三氟乙酸定量产生氢气。动力学研究以及 Co(II)Co(III)-氢化物配合物的检测揭示了 1(+) 与三氟乙酸反应制氢的机制。

更新日期：2013-10-01

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