Departament de Química and Serveis Tècnics de Recerca (STR), Universitat de Girona, Campus de Montilivi, E-17071, Girona, Spain.
Dalton Trans. 2011 Apr 14;40(14):3640-6. doi: 10.1039/c0dt00964d. Epub 2011 Mar 8.
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)(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.
双(2-吡啶基)乙胺(bpea)配体已被用作合成双核 Ru 配合物的起始原料，其通式为 trans,fac-{Ru(n)X(bpea)(μ-bpp)}(m+)（其中 X = Cl，n = II，m = 1，trans-Ru(II)-Cl，1(+)；X = OH，n = III，m = 3，trans-Ru(III)-OH，2(3+)），其中 3,5-双(2-吡啶基)吡唑啉阴离子配体(bpp)作为桥联双核配体，bpea 配体以面式配位，X 为单齿配体以反式方式彼此相邻。这些配合物在溶液中通过 1D 和 2D NMR 光谱、UV-vis 和电化学技术以及在固态下通过 X 射线衍射分析进行了表征。1(PF(6))与 Ag(+)反应生成相应的溶剂化配合物，其中 Cl 配体被不溶性的 AgCl 去除，然后 Ru(II)被氧化为 Ru(III)，生成相应的双核配合物 trans-Ru(III)-OH，2(PF(6))(3)。后者已被证明可使用 Ce(IV)作为氧化剂催化水氧化为分子氧。通过压力计和质谱（MS）技术在线监测了定量的气体随时间的释放。氧形成的相对初始速度以及结构考虑排除了分子内 O-O 键形成途径。
