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57 Fe-Mössbauer Spectroscopic Study of Ferrocenylruthenocene, [1](1,1′)Ferroceno[1](1,1′)ruthenocenophane, and Reaction Products with Some Oxidizing Agents

1990; Oxford University Press; Volume: 63; Issue: 3 Linguagem: Inglês

10.1246/bcsj.63.777

1348-0634

Masanobu Watanabe, Hirotoshi Sano,

Muon and positron interactions and applications

Abstract Ferrocenylruthenocene reacts with sulfuric acid–NH4BF4 to give a mono-oxidized diamagnetic ferrocenylruthenocenium BF4− salt, while it reacts with p-benzoquinon–BF3(Et2O) to give a trioxidized paramagnetic ferrocenylruthenocenium (BF4−)3 salt. Mössbauer parameters of the former salt are very similar to those of neutral ferrocenylruthenocene, suggesting that the structure of the salt is expressed as [Cp(C5H4)Fe(II)(C5H4)CpRu(III)–Ru(III)Cp(C5H4)Fe(II)(C5H4)Cp]2+(BF4−)2 with an antiferromagnetic Ru(III)–Ru(III) bond in the solid state. Well-dissolved quadrupole splitting (Q.S.) values observed for the latter salt (e.g., 0.61mm s−1 at 4.2 K) suggest the presence of a kind of intramolecular electronic effect of a ruthenocenium moiety on the Fe(III) in the ferrocenium moiety.