Structural and electrochemical comparison of trinuclear ruthenium oxo clusters [Ru3(OAc)6O(L)3]+and [Ru3(OAc)6O(L)2(CO)] (L = imidazole, benzimidazole, and 4-phenylpyridine)
| Autor: | Amanda Eckermann, Lindsey Porter, Morgan Glover, Brandon Derstine, Carmen E. Chamberlain |
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| Rok vydání: | 2018 |
| Předmět: |
Benzimidazole
010405 organic chemistry chemistry.chemical_element Metal carbonyl Crystal structure 010402 general chemistry Condensed Matter Physics 01 natural sciences Medicinal chemistry 0104 chemical sciences Ruthenium Inorganic Chemistry chemistry.chemical_compound chemistry Hexafluorophosphate Materials Chemistry Imidazole Physical and Theoretical Chemistry Cyclic voltammetry Acetonitrile |
| Zdroj: | Acta Crystallographica Section C Structural Chemistry. 74:1487-1494 |
| ISSN: | 2053-2296 |
| DOI: | 10.1107/s2053229618013451 |
| Popis: | The triruthenium oxo clusters [Ru3(OAc)6O(L)3]+ and [Ru3(OAc)6O(L)2(CO)] possess unique electronic characteristics that vary based on the ligands L. Here we report an investigation of the structural, electrochemical, and optical properties of clusters with imidazole, benzimidazole, and 4-phenylpyridine ligands. The complexes [Ru3(OAc)6O(L)3]+ [1+ : L = imidazole (im); 2+ : L = benzimidazole (benzim); 3+ : L = 4-phenylpyridine (4PP)] and [Ru3(OAc)6O(L)2(CO)] (1-CO and 3-CO) were synthesized by reaction of either [Ru3(OAc)6O(MeOH)3]+ or [Ru3(OAc)6O(MeOH)2(CO)], respectively, with the corresponding heterocycle. We further discovered that [3]OAc could be reduced to the mixed-valence neutral state 3 by refluxing the complex under nitrogen in methanol. Single-crystal X-ray structure analysis of hexa-μ2-acetato-μ3-oxido-tris(1H-imidazole)triruthenium hexafluorophosphate acetonitrile hemisolvate, [Ru3(C2H3O2)6O(C3H4N2)3]PF6·0.5CH3CN, [1]PF6 , hexa-μ2-acetato-carbonylbis(1H-imidazole)-μ3-oxido-triruthenium methanol monosolvate, [Ru3(C2H3O2)6O(C3H4N2)(CO)]·CH3OH, 1-CO, hexa-μ2-acetato-μ3-oxido-tris(4-phenylpyridine)triruthenium pentahydrate, [Ru3(C2H3O2)6O(C11H9N)3]·5H2O, 3, and hexa-μ2-acetato-carbonyl-μ3-oxido-bis(4-phenylpyridine)triruthenium methanol monosolvate, [Ru3(C2H3O2)6O(C11H9N)2(CO)]·CH3OH, 3-CO, show the expected triruthenium μ3-oxo core and N-coordination of the ligands. Cyclic voltammetry revealed quasi-reversible and irreversible redox couples in [1]PF6 , 1-CO, and [2]PF6 , while [3]PF6 and 3-CO exhibit reversible redox couples. The optical properties of these richly colored species were investigated using UV–Vis spectroscopy. |
| Databáze: | OpenAIRE |
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