Dicationic Thiolate-Bridged Diruthenium Complexes for Catalytic Oxidation of Molecular Dihydrogen
Dicationic Thiolate-Bridged Diruthenium Complexes for Catalytic Oxidation of Molecular Dihydrogen
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DOI：
10.1021/acs.organomet.7b00764
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发表时间：
2017-11
期刊：
影响因子：
2.8
通讯作者：
M. Yuki;Ken Sakata;K. Nakajima;Syoma Kikuchi;Shinobu Sekine;Hiroyuki Kawai;Y. Nishibayashi
中科院分区：
文献类型：
--
作者：
M. Yuki;Ken Sakata;K. Nakajima;Syoma Kikuchi;Shinobu Sekine;Hiroyuki Kawai;Y. Nishibayashi
在硫醇盐配体上带有空间体积大的烷烃取代基的双阳离子硫醇盐桥联的双钌配合物如[Cp*Ru（μ-SiPr）2 Ru（OH 2）Cp*]（OTf）2已被发现作为有效的催化剂用于在质子溶剂如水和甲醇中氧化分子二氢为质子和电子。密度泛函理论计算表明，配合物中的空间位阻较大的烷烃取代基在促进分子二氢配位反应步骤中起着重要作用。
Dicationic thiolate-bridged diruthenium complexes bearing sterically bulky alkane substituents on the thiolate ligands such as [Cp*Ru(μ-SiPr)2Ru(OH2)Cp*](OTf)2 have been found to work as effective catalysts toward oxidation of molecular dihydrogen into protons and electrons in protic solvents such as water and methanol. DFT calculations indicate that the sterically bulky alkane substituent in the complex plays an important role in facilitating the reaction step of the coordination of molecular dihydrogen.