A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH.
A new dinuclear Ru-Hbpp based water oxidation catalyst with a trans-disposition of the Ru-OH.
复制标题
一种新型双核 Ru-Hbpp 基水氧化催化剂，具有 Ru-OH 的反式配置。
作者：
Joaquim Mola;Chiara Dinoi;X. Sala;Montserrat Rodríguez;I. Romero;T. Parella;X. Fontrodona;A. Llobet
国际清算银行以2-吡啶基乙胺（bpea）配体为原料合成了通式为trans，fac-{[Ru（n）X（bpea）]（2）（μ-bpp）}（m+）的双核钌配合物（对于X = Cl，n = II，m = 1，trans-Ru（II）-Cl，1（+）;对于X = OH，n = III，m = 3，反式-Ru（III）-OH，2（3+）），其中3，5-双（2-吡啶基）吡唑阴离子配体（bpp）作为桥联双核配体，bpea配体以面式配位，单齿配体X以反式配位。这些配合物已被其特征在于在溶液中通过1D和2D NMR光谱，紫外-可见和电化学技术，并在固体状态下通过X-射线衍射分析。1（PF（6））与Ag（+）的反应生成相应的溶剂化络合物，其中Cl配体已作为不溶性AgCl被除去，随后Ru（II）氧化成Ru（III）以生成相应的双核络合物trans-Ru（III）-OH，2（PF（6））（3）。后者已经显示出使用Ce（IV）作为氧化剂将水催化氧化成分子双氧。作为时间的函数的定量气体演化已经通过测压和质谱（MS）技术在线监测。氧形成的相对初始速度与结构考虑一起排除了分子内O-O键形成途径。
The bis(2-pyridyl)ethylamine (bpea) ligand has been used as a starting material for the synthesis of dinuclear Ru complexes of general formula trans,fac-{[Ru(n)X(bpea)](2)(μ-bpp)}(m+) (for X = Cl, n = II, m = 1, trans-Ru(II)-Cl, 1(+); for X = OH, n = III, m = 3, trans-Ru(III)-OH, 2(3+)) where the 3,5-bis(2-pyridyl)pyrazolate anionic ligand (bpp) acts as bridging dinucleating ligand, the bpea ligand coordinates in a facial manner and the monodentate ligands X are situated in a trans fashion with regard to one another. These complexes have been characterized in solution by 1D and 2D NMR spectroscopy, UV-vis and electrochemical techniques and in the solid state by X-ray diffraction analysis. The reaction of 1(PF(6)) with Ag(+) generates the corresponding solvated complex where the Cl ligand has been removed as insoluble AgCl, followed by the oxidation of Ru(II) to Ru(III) to generate the corresponding dinuclear complex trans-Ru(III)-OH, 2(PF(6))(3). The latter has been shown to catalytically oxidize water to molecular dioxygen using Ce(IV) as oxidant. Quantitative gas evolution as a function of time has been monitored on line by both manometry and mass spectroscopy (MS) techniques. Relative initial velocities of oxygen formation together with structural considerations rule out an intramolecular O-O bond formation pathway.
影响因子：
15
作者：
Hull JF;Balcells D;Blakemore JD;Incarvito CD;Eisenstein O;Brudvig GW;Crabtree RH
通讯作者：
Crabtree RH