REACTIVITY OF FUNCTIONALIZED CYCLOMETALATED COMPLEXES OF PALLADIUM(II) - CRYSTAL AND MOLECULAR-STRUCTURE OF [PD(3-(CHO)C6H3C(H)=NCY)(BR)(PETPH2)]

Treatment of the cyclometallated complexes [{Pd[3-(CHO)C6H3C(H)=NCy}(X )}(2)] (X = Cl (1), Br (2), I (3)] with tertiary monophosphines in a c omplex/phosphine 1:2 or 1:4 molar ratio afforded the halide-bridged cl eaved [Pd{3-(CHO)C6H3C(H)=NCy}(X)(L)] (6-17) and non-cyclometallated c omplexes [Pd{3-(CHO)C6H3C(H)=NCy}(X)(L)(2)] (18-23) (X = Cl, Br or I; L = PPh3, PEtPh2, PEt2Ph or PMePh2), respectively. Reaction of 6-17 wi th cyclohexylamine in a complex/amine 1:1 or 1:2 molar ratio gave [Pd{ 3-(CyC(H)=N)C6H3C(H)=NCy}(X)(L)] (24-28) and the non-cyclometallated [ Pd{3-(CyC(H)=N)C6H3C(H)=NCy}(X)(L)(NH2Cy)] (29-32) complexes, respecti vely. Compounds 18, 19 and 22 gave [Pd{3-(CyC(H)=N)C6H3C(H)=NCy}(X)(PR 3)(2)] (33-35) with two uncoordinated C=N groups, when treated with cy clohexylamine. Other reaction routes are also discussed. The complexes were characterised by their elemental analysis (C, H, N) and by IR an d P-31{H-1} and H-1-NMR data, and [Pd{3-(CHO)(C6H3C(H)=NCy}(Br)(PEtPh2 )] (12) was characterised crystallographically. (C) 1998 Elsevier Scie nce S.A. All rights reserved.