Ruthenium(ii) and ruthenium(iv) complexes containing hemilabile heterodifunctional iminophosphorane-phosphine ligands Ph2PCH2P(NR)Ph2

The dimeric complex [{Ru(η6-p-cymene)(μ-Cl)Cl}2] reacts with iminophosphorane-phosphine ligands Ph2PCH2P(NR)Ph2 (R = SiMe31, p-C6F4CN 2, p-C5F4N 3), in dichloromethane at room temperature, to afford the neutral derivatives [Ru(η6-p-cymene)Cl2{κ1-P-Ph2PCH2P(NR)Ph2}] (R = SiMe34, p-C6F4CN 5, p-C5F4N 6). Treatment of 4–6 with NaPF6 in methanol allows the preparation of cationic species [Ru(η6-p-cymene)Cl{κ2-P,N-Ph2PCH2P(NR)Ph2}][PF6] (R = H 7, p-C6F4CN 8, p-C5F4N 9). While complexes 8 and 9 react with anionic ligands yielding neutral derivatives [Ru(η6-p-cymene)X2{κ1-P-Ph2PCH2P(NR)Ph2}] (R = p-C6F4CN, X = Br 10a, I 10b, N310c, CN 10d, NCO 10e; R = p-C5F4N, X = Br 11a, I 11b, N311c, CN 11d, NCO 11e), cationic species [Ru(η6-p-cymene)X{κ2-P,N-Ph2PCH2P(NH)Ph2}][PF6] (X = Br 12a, I 12b, N312c, 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(η6-p-cymene)Cl(PR3){κ1-P-Ph2PCH2P(NR)Ph2}][PF6] (R = p-C6F4CN, PR3 = PMe313a, PMe2Ph 13b, PMePh213c, PPh313d; R = p-C5F4N, PR3 = PMe314a, PMe2Ph 14b, PMePh214c, PPh314d), [Ru(η6-p-cymene)Cl(py){κ1-P-Ph2PCH2P(NR)Ph2}][PF6] (R = p-C6F4CN 15; R = p-C5F4N 16), [Ru(η6-p-cymene)Cl(NCMe){κ1-P-Ph2PCH2P(NR)Ph2}][PF6] (R = p-C6F4CN 17; R = p-C5F4N 18) and [Ru(η6-p-cymene)Cl(CNR′){κ1-P-Ph2PCH2P(NR)Ph2}][PF6] (R = p-C6F4CN, R′ = Cy 19a, 2,6-C6H3Me219b; R = p-C5F4N, R′ = Cy 20a, 2,6-C6H3Me220b), respectively. The synthesis of complexes [Ru(η3:η3-C10H16)Cl2{κ1-P-Ph2PCH2P(NR)Ph2}] (R = SiMe321, p-C6F4CN 22, p-C5F4N 23) and [Ru(η3:η3-C10H16)Cl{κ2-P,N-Ph2PCH2P(NH)Ph2}][BF4] 24 starting from the bis(allyl)-ruthenium(IV) dimer [{Ru(η3:η3-C10H16)(μ-Cl)Cl}2] and ligands 1–3 is also reported.