Cyclopalladated compounds with bridging and chelating diphosphine ligands.: Effect of ring size.: Crystal and molecular structure of [{Pd[4-(COH)C6H3C(H)=N(Cy)-C2,N](Cl)}2(μ-Ph2PCH2PPh2)]

Treatment of the chloro-bridged dinuclear compound [{Pd[4-(COH)C6H3C(H)=N(Cy)-C2,N]}(mu-Cl)](2) (1) with tertiary diphosphines in 1:1 molar ratio gave [ Pd[4-(COH)C6H3C(H)=N(Cy)-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; Cequivalent toC, 8) with the diphosphine in a bridging mode. When the reaction was carried out in a 1:2 molar ratio in the presence of NH4PF6, the compounds [Pd{4-(COH)C6H3C(H)=NCy-C-2,N}(Ph2PRPPh2-P,P)][PF6] (R: CH2, 9; CH2CH2, 10; (CH2)(4), 11; (CH2)(6),12; Fe(C5H4)(2),13; 1,2-C6H4,14; cis-CH=CH, 15; NH, 16) with the diphosphine chelated to the palladium atom, were obtained. H-1 P-31-{H-1} and C-13-{H-1} NMR, IR and mass spectroscopic data are given. The crystal structure of compound 2 has been determined by X-ray crystallography. equivalent to(C) 2002 Elsevier Science Ltd. All rights reserved.