1H, 13C-NMR and 57Fe-Mössbauer spectroscopic studies of α,α-ferrocenylruthenocenylmethylium + ion

Abstract

Ferrocenylruthenocenylmethane reacts with chloro- or bromoruthenocenium(IV) + PF 6 − salts, giving a deep-purple salt. The results of 57Fe-Mössbauer, 1H, and 13C NMR spectroscopic studies on the salt suggest the formula α,α-ferrocenylruthenocenylmethylium hexafluorophosphate salt; [Fe IICp(C 5H 4CH +C 5H 4)CpRu II]PF 6 − ( 1). The salt gives remarkably temperature dependent 1H and 13C NMR spectra, due to rotation about the exocyclic carbon atom (-CH +-). The energy barrier of the rotation is estimated on the basis of 1H NMR line simulation studies to be about 34.0 ± 0.6 kJ mol −1. On the other hand, ferrocenylruthenocenylmethane reacts with iodoruthenocenium(IV) +Y − (Y; BF 4, PF 6) salts, giving paramagnetic dicationic salts formulated from the results of 57 Fe-Mössbauer and NMR spectroscopic studies as [Fe IIICp(C 5H 4CH 2C 5H 4)CpRu IV I] 2+Y 2 −.