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}(mu-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)(mu-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).H-1 P-31{H-1} and C-13{H-1}-NMR, IR and mass spectral data are given. The crystal structures of compounds 2-4 have been determined by X-Ray crystallography. (C) 2002 Elsevier Science B.V. All rights reserved.