%0 Journal Article %1 Sixt.2010 %A Sixt, Torsten %A Sieger, Monika %A Krafft, Michael J. %A Bubrin, Denis %A Fiedler, Jan %A Kaim, Wolfgang. %D 2010 %J Organometallics %K bridging chloride crystal cymene dichloro dimer diphosphinoferrocene diphosphinoferrocene;para diphosphinoferrocene;pentamethylcyclopentadienyl half heterodimetallic hydride hydride;ruthenium para prepn;mol ruthenium sandwich structure %N 21 %P 5511--5516 %R 10.1021/om1004258 %T 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 \dqMixed-Valent\dq Intermediates %V 29 %X Combining two different redox-active organometallic moieties, we prepd. the compds. (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 approx. 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 soln. The related new compds. (Cym)RuH(dppf)(PF6) (6) and trinuclear (m-dpf)(Cym)RuCl22 (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, spectroelectrochem. in the UV/vis/near-IR and IR regions, and, in part, by EPR. The first oxidn. of the areneruthenium compds. 3-6 occurs reversibly at the ferrocene site, while the redn. proceeds via an ECE two-electron pattern under chloride dissocn. These results are compared to those obtained for the pentamethylcyclopentadienide/hydride complexes 1 and 2, which demonstrate unambiguously the ruthenium center as the site of the first electron loss. The different results for the two kinds of heterodimetallic d5/d6 mixed-valent intermediates, FeIIRuIII for 1+ and 2+ and FeIIIRuII for 3+-6+, are discussed with respect to the possible uses of such heterodinuclear systems in H2 conversion catalysis. on SciFinder(R)

@article{Sixt.2010, abstract = {Combining two different redox-active organometallic moieties, we prepd. the compds. [(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 approx. 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 soln. The related new compds. [(Cym)RuH(dppf)](PF6) (6) and trinuclear (\textgreek{m}-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, spectroelectrochem. in the UV/vis/near-IR and IR regions, and, in part, by EPR. The first oxidn. of the areneruthenium compds. 3-6 occurs reversibly at the ferrocene site, while the redn. proceeds via an ECE two-electron pattern under chloride dissocn. These results are compared to those obtained for the pentamethylcyclopentadienide/hydride complexes 1 and 2, which demonstrate unambiguously the ruthenium center as the site of the first electron loss. The different results for the two kinds of heterodimetallic d5/d6 mixed-valent intermediates, FeIIRuIII for 1+ and 2+ and FeIIIRuII for 3+-6+, are discussed with respect to the possible uses of such heterodinuclear systems in H2 conversion catalysis. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Sixt, Torsten and Sieger, Monika and Krafft, Michael J. and Bubrin, Denis and Fiedler, Jan and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/22a558978a74b5153ce8d55b63d97f0fe/huebleriac}, doi = {10.1021/om1004258}, interhash = {b876865a23108f628f20a53e5b0c3fb1}, intrahash = {2a558978a74b5153ce8d55b63d97f0fe}, issn = {0276-7333}, journal = {Organometallics}, keywords = {bridging chloride crystal cymene dichloro dimer diphosphinoferrocene diphosphinoferrocene;para diphosphinoferrocene;pentamethylcyclopentadienyl half heterodimetallic hydride hydride;ruthenium para prepn;mol ruthenium sandwich structure}, number = 21, pages = {5511--5516}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {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 {\dq}Mixed-Valent{\dq} Intermediates}, volume = 29, year = 2010 }