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

Abstract

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.