The dimeric complex [{Ru(eta(6)-p-cymene)(mu-Cl)Cl}(2)] reacts with iminophosphorane-phosphine ligands Ph2PCH2P(=NR)Ph-2 (R = SiMe3 1, p-C6F4CN 2, p-C5F4N 3), in dichloromethane at room temperature, to afford the neutral derivatives [Ru(eta(6)-p-cymene)Cl-2{kappa(1)-P-Ph2PCH2P(=NR)Ph-2}] (R = SiMe3 4, p-C6F4CN 5, p-C5F4N 6). Treatment of 4-6 with NaPF6 in methanol allows the preparation of cationic species [Ru(eta(6)-p-cymene)Cl{kappa(2)-P,N-Ph2PCH2P(=NR)Ph-2}][PF6] (R = H 7, P-C6F4CN 8, p-C5F4N 9). While complexes 8 and 9 react with anionic ligands yielding neutral derivatives [Ru(eta(6)-p-cymene)X-2{kappa(1)-P-Ph2PCH2P(=NR)Ph-2}] (R = p-C6F4CN, X = Br 10a, I 10b, N-3 10c, CN 10d, NCO 10e; R = p-C5F4N, X = Br 11a, I 11b, N-3 I 11c, CN 11d, NCO 11e), cationic species [Ru(eta(6)-p-cymene)X{kappa(2) -P,N-Ph2PCH2P(=NH)Ph-2}][PF6] (X = Br 12a, I 12b, N-3 12c, CN 12d, NCO 12e) are exclusively formed starting from 7. Complexes 8 and 9 also react with neutral ligands such as phosphines, pyridine, acetonitrile or isocyanides affording compounds [Ru(eta(6) -p-cymene)Cl(PR3){kappa(1)-P-Ph(2)PCH(2)p(=NR)Ph-2}][PF6] (R =P-C6F4CN, PR3 = PMe3 13a, PMe2Ph 13b, PMePh2 13c, PPh3 13d; R = p-C5F4N, PR3 = PMe3 14a, PMe2Ph 14b, PMePh2 14c, PPh3 14d), [Ru(eta(6)-p-cymene)Cl(py){kappa(1)-P-Ph2PCH2P(=NR)Ph-2}][PF6] (R =p-C6F4CN 15; R = p-C5F4N 16), [Ru(eta(6)-p-cymene)Cl(N=CMC) {kappa(1)-P-Ph2PCH2P(=NR)Ph-2}][PF6] (R = p-C6F4CN 17; R = p-C5F4N 18) and [Ru(eta(6)-p-cymene)Cl(CNR'){kappa(1)-P-Ph2PCH2P(=NR)Ph-2}][PF6] (R =P-C6F4CN, R' = Cy 19a, 2,6-C6H3Me2 19b; R = p-C5F4N, R' = Cy 20a, 2,6-C6H3Me2 20b), respectively. The synthesis of complexes [Ru(eta(3):eta(3)-C10H16)Cl-2{kappa(1)-P-Ph2PCH2P(=NR)Ph-2}] (R = SiMe3 21, p-C6F4CN 22, p-C5F4N 23) and [Ru(eta(3):eta(3)-C10H16)Cl{kappa(2)-P,N-Ph2PCH2P(=NH)Ph-2}][BF4] 24 starting from the bis(allyl)-ruthenium(IV) dimer [{Ru(eta(3):eta(3)-C10H16)(mu-Cl)Cl}(2)] and ligands 1-3 is also reported.