Versatile reactivity of cyclic 1,2-dimethylhydrazinodiphosphines

International audience; A versatile reactivity from the cage compound P(NMeNMe)3P is presented. The Staudinger reaction with Me3SiN3 is carried out. The crystal structure of the compound issued from the reaction on both sides (Me3SiN=P(NMeNMe)3P=NSiMe3) is reported. When the reaction occurs on only one side, the remaining free phosphorus atom is complexed with RuCl2(p-cymene). P(NMeNMe)3P reacts with PCl3, leading to the heterocyclic compound ClP(NMeNMe)2PCl. This heterocycle also displays a versatile reactivity. Substitution reaction with HNiPr2 leads to iPr2NP(NMeNMe)2PNiPr2. Very complex 1H and 13C NMR spectra suggest that the cis isomer is the largely major isomer of this compound. The cis structure is confirmed by X-ray diffraction. Besides the reaction on the P–Cl functions, the reaction on the lone pair of ClP(NMeNMe)2PCl is carried out, leading to the complex (p-cymene)Cl2RuPCl(NMeNMe)2ClPRuCl2(p-cymene). Characterization of this compound by X-ray diffraction displays a cis isomer for this compound also.