Hoque Md Asmaul, Gil-Sepulcre Marcos, Benet-Buchholz Jordi, Llobet Antoni, Gimbert-Suriñach Carolina
Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain.
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Campus Sescelades, C/Marcel·lí Domingo, s/n, 43007 Tarragona, Spain.
Inorg Chem. 2020 Aug 17;59(16):11432-11441. doi: 10.1021/acs.inorgchem.0c01215. Epub 2020 Aug 3.
The tridentate meridional ligand pyridyl-2,6-dicarboxylato (pdc) has been used to prepare complexes [Ru(pdc-κ-NO)(DMSO)Cl] (), [Ru(pdc-κ-NO)(bpy)(DMSO)] (), and {Ru(pdc-κ-NO)(bpy)} (), where bpy = 2,2'-bipyridine. All complexes have been fully characterized through spectroscopic, electrochemical, and single-crystal X-ray diffraction techniques. Compounds and show S → O linkage isomerization of the DMSO ligand upon oxidation from Ru to Ru, and thermodynamic and kinetic data have been obtained from cyclic voltammetry experiments. Dimeric complex is a precursor of the monomeric complex [Ru(pdc-κ-NO)(bpy)(HO)] () which is a water oxidation catalyst. The electrochemistry and catalytic activity of has been ascertained for the first time and compared with related Ru-aquo complexes that are also active for the water oxidation reaction. It shows a TOF = 0.2 s and overpotential of 240 mV in pH = 1. The overpotential shown by is one of the lowest reported in the literature and is associated with the role of the two carboxylato groups of the pdc ligand, providing high electron density to the ruthenium complex.
三齿经向配体吡啶基-2,6-二羧酸根（pdc）已用于制备配合物[Ru(pdc-κ-NO)(DMSO)Cl]（）、[Ru(pdc-κ-NO)(bpy)(DMSO)]（）和{Ru(pdc-κ-NO)(bpy)}（），其中bpy = 2,2'-联吡啶。所有配合物均已通过光谱、电化学和单晶X射线衍射技术进行了全面表征。化合物和在从Ru氧化为Ru时显示出DMSO配体的S→O键异构化，并且已从循环伏安实验中获得了热力学和动力学数据。二聚配合物是单体配合物[Ru(pdc-κ-NO)(bpy)(HO)]（）的前体，该单体配合物是一种水氧化催化剂。首次确定了的电化学和催化活性，并与对水氧化反应也有活性的相关钌水合配合物进行了比较。在pH = 1时，它的TOF = 0.2 s，过电位为240 mV。所显示的过电位是文献中报道的最低值之一，并且与pdc配体的两个羧酸根基团的作用有关，为钌配合物提供了高电子密度。
