57Fe-Moessbauer spectroscopic study of ferrocenylruthenocene, (1)(1,1')ferroceno(1)(1,1')ruthenocenophane, and reaction products with some oxidizing agents.

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概要

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• Ferrocenylruthenocene reacts with sulfuric acid–NH<SUB>4</SUB>BF<SUB>4</SUB> to give a mono-oxidized diamagnetic ferrocenylruthenocenium BF<SUB>4</SUB><SUP>−</SUP> salt, while it reacts with <I>p</I>-benzoquinon–BF<SUB>3</SUB>(Et<SUB>2</SUB>O) to give a trioxidized paramagnetic ferrocenylruthenocenium (BF<SUB>4</SUB><SUP>−</SUP>)<SUB>3</SUB> 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(C<SUB>5</SUB>H<SUB>4</SUB>)Fe(II)(C<SUB>5</SUB>H<SUB>4</SUB>)CpRu(III)–Ru(III)Cp(C<SUB>5</SUB>H<SUB>4</SUB>)Fe(II)(C<SUB>5</SUB>H<SUB>4</SUB>)Cp]<SUP>2+</SUP>(BF<SUB>4</SUB><SUP>−</SUP>)<SUB>2</SUB> 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<SUP>−1</SUP> 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.

• 公益社団法人 日本化学会の論文

著者

• Watanabe Masanobu

  Department Of Applied Chemistry Faculty Of Engineering Kanagawa University

• Sano Hirotoshi

  Department of Chemistry Faculty of Science The University of Tokyo

• Sano Hirotoshi

  Deparment of Chemistry, Faculty of Science, Tokyo Metropolitan University

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