[3]- and [4]ruthenocenophanes as well as other ruthenocene derivatives were synthesized. The preparation of ruthenocenes in this experiment required more forced reaction conditions than those of the corresponding ferrocenes. Two cyclopentadienyl rings of these ruthenocenophanes are found to tilt mutually, and the degree of the ring-tilting of [3]ruthenocenophane is greater than that of the [4] homolog.

Stereochemistry in the hydrogenation of 4-t-butylcyclohexanone and the corresponding oxa- and dioxacyclohexanone was examined. A high cis selectivity was observed in the latter two compounds regardless of the catalyst metals used here. These results were explained in terms of intramolecular nO–πCO interaction, which was supported by 13C NMR chemical shifts of the carbonyl carbons and CNDO/2 calculation.

The reaction between (dimethylaminomethyl)ruthenocene with lithium tetrachloropalladate(II) in the presence of sodium acetate gave di-μ-chloro-bis[2-(dimethylaminomethyl)ruthenocenyl]dipalladium(II) (2). The σ-bonded structure of 2 has been confirmed by IR analysis and the reactions of 2 with triphenylphosphine, thallium(I) acetylacetonate, and lithium aluminum deuteride. The reactions of chloro [2-(dimethylaminomethyl)ruthenocenyl](triphenylphosphine)palladium(II) with carbon monoxide and 2 with methyl vinyl ketone, phenyl vinyl ketone, and styrene have been examined. 1,2-Disubstituted ruthenocene derivatives have been obtained in higher yields than those of the corresponding ferrocene derivatives.

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