Cyclometallated complexes of Pd(II) with heterobidentate P, As and P, N coordinating ligands

Treatment of the choride-bridged dimer [Pd{4-(COH)C6H3C(H)N(Cy)C2,N}(μ-Cl)]2 (1), with Ph2PCH2CH2AsPh2 (arphos) in 1:1 molar ratio in acetone gave the dinuclear complex [{Pd[4-(COH)C6H3C(H)N(Cy)C2,N](Cl)}2(μ-Ph2PCH2CH2AsPh2)] (2), with the arsinophosphine as a bridging ligand, and in 1:2 molar ratio in the presence of NH4PF6 gave the mononuclear compound [Pd{4-(COH)C6H3C(H)N(Cy)C2,N}(Ph2PCH2CH2AsPh2P,As)][PF6], (3), with the arsinophosphine chelated to the metal center. Reaction of 1 with Ph2PCH2CH2CH2NH2 in 1:2 molar ratio in acetone and NH4PF6 afforded [Pd{4-(COH)C6H3C(H)N(Cy)C2,N}{Ph2PCH2CH2CH2N(CMe2)P,N}][PF6] (4), after intermolecular condensation between the aminophosphine and the solvent. Condensation was precluded by treatment in toluene to give the mononuclear compound [Pd{4-(COH)C6H3C(H)N(Cy)C2,N}(Ph2PCH2CH2CH2NH2P,N)][PF6], (5). 1H, 31P{1H} and 13C{1H}-NMR, IR and mass spectral data are given. The crystal structures of compounds 2–4 have been determined by X-Ray crystallography.