Ambi-Valence Taken Literally: Ruthenium vs Iron Oxidation in (1,1′-Diphosphinoferrocene)ruthenium(II) Hydride and Chloride Complexes as Deduced from Spectroelectrochemistry of the Heterodimetallic 'Mixed-Valent' Intermediates
| Autor: | Michael J. Krafft, Monika Sieger, Jan Fiedler, Wolfgang Kaim, Denis Bubrin, Torsten Sixt |
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| Rok vydání: | 2010 |
| Předmět: | |
| Zdroj: | Organometallics. 29:5511-5516 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | Combining two different redox-active organometallic moieties, we prepared the compounds [(Cym)RuCl(dpf)](PF6), with Cym = p-cymene = 1-isopropyl-4-methylbenzene, and the diphosphinoferrocenes (dpf) 1,1′-bis(diphenylphosphino)ferrocene (dppf; complex 3), 1,1′-bis(diisopropylphosphino)ferrocene (dippf; complex 4), and 1,1′-bis(diethylphosphino)ferrocene (depf; complex 5) as well as the structurally characterized hydride complex [(C5Me5)RuH(dippf)] (2). In contrast to the case for 2, with an approximately staggered ferrocene conformation, the chloride complexes 3−5 exhibit a syn-periplanar ferrocene arrangement due to a Cl···H(C5H4) interaction in the solid and in solution. The related new compounds [(Cym)RuH(dppf)](PF6) (6) and trinuclear (μ-dpf)[(Cym)RuCl2)]2 (7−9) were also obtained and identified by 1H and 31P NMR spectroscopy. The redox behavior of 2−6 and of the known [(C5Me5)RuH(dppf)] (1) was investigated using cyclic voltammetry, spectroelectrochemistry in the UV/vis/near-IR and IR regions, and, in ... |
| Databáze: | OpenAIRE |
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