Abstract
Diruthenocenylketone (RcCORc, 1) as a precursor of diruthenocenylmethane (RcCH 2Rc, 2), was first prepared in 30% yield in a one-step reaction of ruthenocene (RcH) with butyllithium (BuLi) and N, N-dimethylcarbamyl chloride. Reaction of 2 with I 2 and iodoruthenocenium(IV) +PF 6 − ([RcHI] +PF 6 −) gives mixed valence salts formulated as [Ru IICp(C 5H 4CH 2C 5H 4)CpRu IVI] +Y − (Y=I 3 ( 3), PF 6 ( 4)) in which the intramolecular electron exchange reaction associated with iodine migration between the Ru II and Ru IV atoms is observed. The activation energy of the reaction ( E a) is estimated to be 31.0±0.6 kJ mol −1 for 3 in acetone, which is smaller than the corresponding value of a mixed valence [RcRcI] +I 3 − salt (36.5±0.6 kJ mol −1). Reaction of 2 with the [RcHCI] +PF 6 − or [RcHBr] +PF 6 − salts gives an α,α-diruthenocenylmethylium +PF 6 − salt formulated as [Ru IICp(C 5H 4CH +H 4C 5)CpRu II]PF 6 − ( 5).
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