Regulation of electron donating ability to metal center: isolation and characterization of ruthenium carbonyl complexes with N,N- and/or N,O-donor polypyridyl ligands |
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| Institution: | 1. Faculty of Education, Fukushima University, Kanayagawa, Fukushima 960-1296, Japan;2. Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan;3. CREST, Japan Science and Technology Corporation (JST), Tokyo, Japan;1. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150090, China;2. State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China;1. Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 119260, Singapore;2. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore;1. Department of Chemistry, National Dong Hwa University, Hualien 97401, Taiwan;2. A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation;3. Zhejiang Provincial Key Laboratory of Chemical Utilization of Forestry Biomass, Zhejiang A & F University, Lin''an, Zhejiang 311300, PR China |
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| Abstract: | Polypyridyl ruthenium(II) dicarbonyl complexes with an N,O- and/or N,N-donor ligand, Ru(pic)(CO)2Cl2]− (1), Ru(bpy)(pic)(CO)2]+ (2), Ru(pic)2(CO)2] (3), and Ru(bpy)2(CO)2]2+ (4) (pic=2-pyridylcarboxylato, bpy=2,2′-bipyridine) were prepared for comparison of the electron donor ability of these ligands to the ruthenium center. A carbonyl group of Ru(L1)(L2)(CO)2]n (L1, L2=bpy, pic) successively reacted with one and two equivalents of OH− to form Ru(L1)(L2)(CO)(C(O)OH)]n−1 and Ru(L1)(L2)(CO)(CO2)]n−2. These three complexes exist as equilbrium mixtures in aqueous solutions and the equilibrium constants were determined potentiometrically. Electrochemical reduction of 2 in CO2-saturated CH3CN–H2O at −1.5 V selectively produced CO. |
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