PALLADIUM COMPLEXES OF AZINES, ALPHA-DIAZINES AND ALPHA-2-PYRIDYLAZINES CONTAINING (1R)-(+)-CAMPHOR OR (1R)-(-)-FENCHONE GROUPS

Mixed monoazines of types H2C=N-N=C10H16 [C10H16 is a (1R)-(+)-camphor residue (L(1)), or a (1R)-(-)-fenchone residue (L(2))] or Me(2)C=N-N=C10H16 [C10H16 is a (1R)-(+)-camphor residue (L(3))], or alpha-diazines C10H16=N-N=CH-CH=N-N=C10H16 [C10H16 is a (1R)-(+)-camphor residue (L(4)) or a (1R)-(-)-fenchone residue (L(5))], or alpha-2-pyridyl azines C10H16=N-N=CHC5H4N [C10H16 is a (1R)-(+)-camphor residue (L(6)) or a (1R)-(-)-fenchone residue (L(7))] reacted with Na2PdCl4 to give compounds of type [PdCl(2)L(2)(n)] for L(1), L(2) or L(3) as monodentate nitrogen-donor ligands and chelated mononuclear complexes of the type [PdCl(2)L(n)] for L(4), L(5), L(6) or L(7). The complexes of the monodentate azines L(1) and L(2) exist in solution as mixtures of isomers differing in the ligating nitrogens. The compounds L(1), L(2) and L(4)-L(7) also reacted with [Pd2Cl4(PR(3))(2)] to give [PdCl2(PR(3))L(n)] (n=1, R(3)=Me(2)Ph or Me(2)(C(6)H(4)OMe-4); n=2, R(3)=Me(2)Ph, Me(2)(C(6)H(4)OMe-4) or Ph(3); n=4 or 5, R(3)=Me(2)Ph; n=6, R(3)=Bu(3)(n); n=7, R(3)=Bu(3)(n), or Me(2)Ph), in which the ligands are monodentate, or [{PdCl2(PR(3))}(2)L(n)] (L(n)=L(4)-L(7), R(3)=Me(2)Ph), in which the ligands are bidentate bridging. The phosphine complexes were characterised in solution but were isolated only for [PdCl2(PR(3))L(n)] (L(n)=L(6), R(3)=Bu(3)(n); L(7), R(3)=Bu(3)(n) or Me(2)Ph; L(2), R(3)=Ph(3)). Compounds L(4), L(6) or L(7) reacted with the eta(3)-methylallylpalladium complex [{PdCl(eta(3)-CH(2)CMeCH(2))}(2)] and NH4PF6 to give [Pd(eta(3)-CH(2)CMeCH(2))L(n)]PF6 (L(n)=L(4), L(6) or L(7)). The crystal structure of [PdCl(2)L(6)]. 0.5CH(2)Cl(2) was determined by X-ray diffraction analysis: the crystals are monoclinic, space group P2(1) with a=9.5830(13), b=13.9720(14) and c=14.726(2) Angstrom, beta=97.610(11)degrees and Z=4. It shows two molecules of the complex in the asymmetric unit differing only in the torsion angles around the N-N bond.