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Synthesis, characterization and properties of oxo-bridged diruthenium(III) complexes with thiocyanato and cyanato ligands
Oxo-bridged diruthenium(III) complexes with triatomic anion ligands SCN− and OCN− were prepared. The electronic absorption and electrochemical properties were studied and interpreted with the aid of theoretical calculations. The visible absorption bands were attributed to mainly the metal-to-metal c...
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Published in: | Inorganica Chimica Acta 2018-01, Vol.469, p.469-477 |
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Main Authors: | , , , , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
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Online Access: | Get full text |
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Summary: | Oxo-bridged diruthenium(III) complexes with triatomic anion ligands SCN− and OCN− were prepared. The electronic absorption and electrochemical properties were studied and interpreted with the aid of theoretical calculations. The visible absorption bands were attributed to mainly the metal-to-metal charge transfer (MMCT) transitions, on which the solvent effect was strong.
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•Preparation and characterization of oxo-bridged diruthenium complexes.•Electronic absorption properties.•Redox chemistry.•Theoretical investigation.
The oxo-bridged diruthenium(III) complexes with thiocyanato and cyanato ligands, trans(μ-O,L)-[Ru2(μ-O)(μ-CH3COO)2(bpy)2(L)2] (bpy=2,2′-bipyridine; L=SCN− (1); OCN− (2)), have been synthesized, characterized, and their properties studied. X-ray single crystallography revealed that the thiocyanato ligands of 1 are N-bonded to the Ru centers at the trans sites to the oxo-bridge. The OCN− ligand in 2 is also N-bonded based on the infrared spectroscopy. The cyclic voltammograms of 1 and 2 in dimethyl sulfoxide (DMSO) solutions of 0.1M (n-Bu)4NPF6 showed two redox couples at around −0.5V and +0.5Vvs Ag/AgCl, which were assigned to the processes Ru2III,III/Ru2III,II and Ru2IV,III/Ru2III,III, respectively. The electronic absorption spectra of 1 and 2 in CH3CN solutions showed strong absorption bands at 625 and 637nm, respectively. The bands showed a remarkable blueshift in H2O to 578 and 581nm as a consequence of the solvent interactions at the free end of the thiocyanato and cyanato ligands, respectively. The theoretical calculations of both 1 and 2 and also their coordination isomers (N-bonded and S-bonded for the thiocyanate complex, and N-bonded and O-bonded for the cyanate complex) revealed that the N-bonded isomers are energetically more stable. Both the SCN− and OCN− ligands are primarily good σ donors to the Ru2O core. The contributions of SCN− to the dπ(Ru)–pπ(μ-O) conjugated system are particularly significant (>20%). The strong visible absorption bands of both 1 and 2 were attributed to mainly the metal-to-metal charge transfer (MMCT) transitions with some contributions from the ligand (SCN−, OCN−)-to-ligand (μ-O) charge transfer (LLCT). |
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ISSN: | 0020-1693 1873-3255 |
DOI: | 10.1016/j.ica.2017.09.053 |