Functionalized cyclopalladated compounds with bidentate Group 15 donor atom ligands:: the crystal and molecular structures of [{Pd[5-(COH)C6H3C(H)=NCy-C2,N](Cl)}2(μ-Ph2PRPPh2)] (R = CH2CH2, Fe(C5H4)2], [Pd{5-(COH)C6H3C(H)=NCy-C2,N}(Ph2PCH2PPh2-P,P)][PF6] and [Pd{5-(COH)C6H3C(H)=N(Cy)-C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6]

The chloro-bridged dinuclear compound [{Pd[5-(COH)C6H3C(H) =N(Cy)-C2,N]}(mu-Cl)](2) (1), reacts with tertiary diphosphines in 1:1 molar ratio to give [{Pd[5-(COH)C6H3C(H)=NCy-C2,N](Cl)}(2)(mu-Ph2PRPPh2)] (R: CH2,2; CH2CH2,3; (CH2)(4),4; (CH2)(6),5; Fe(C5H4)(2), 6; trans-CH=CH, 7; C drop C, 8). Treatment of 1 with Ph2PCH2CH2AsPh2 (arphos) gives the dinuclear complex [{Pd[(5)(COH)C6H3C(H)=N(Cy)-C2,N](Cl)}(2)(mu-Ph2PCH2CH2AsPh2)] (9). The reaction of 1 with tertiary diphosphines or arphos in 1:2 molar ratio in the presence of NH4PF6 yields the mononuclear compounds [Pd{5-(COH)C6H3C(H)=NCy-C2,N}(Ph2PRPPh2-P,P)][PF6] (R: (CH2)(4), 10; (CH2)(6), 11; Fe(C5H4)(2),12; 1,2-C6H4,13; cis-CH=CH, 14; NH, 15) and [Pd{5-(COH)C6H3C(H)=N(Cy)-C2,N}(Ph2PCH2CH2AsPh2-P,As)][PF6](16). H-1-, P-31-{H-1}- and C-13-{H-1}-NMR, IR and mass spectroscopic data are given. The crystal structures of compounds 3, 6, 9 and 16 have been determined by X-ray crystallography. (C) 2002 Elsevier Science B.V. All rights reserved.