Organometallic chemistry of diphosphazanes. Part 19 -Palladium-carbon sigma-bonded complexes bearing diphosphazane and diphosphazane monosulphide ligands

The reactions of the diphosphazanes and diphosphazane monosulphides, Ph2P(E)N(R)PPh2 [E = lone pair, R = CHMe2 (1); E = lone pair, R = (S)-*CHMePh (2); E = S, R = CHMe2 (3); E = S, R = (S)-*CHMePh (4)] with [PdMeCl(COD)] yield the neutral chelate complexes of the type [PdMe{kappa(2)-Ph2P(E)N(R)PPh2}Cl] (5, 6, 8 and 9). The reactions of 1-3 with chlorobridged cyclometallated palladium azobenzene dimers, [Pd{(C6H3-R'-4)-N=N-(C6H4 R'-4)(mu-Cl)](2) (R' = H or OC6H13) in the presence of NH4PF6 yield cationic cyclopalladated complexes, [{kappa(2)-(C6H3-R'-4)-N=N-(C6H4-R'-4)}Pd{kappa(2)-Ph2P(E)N(R)PPh2}](PF6) (10-15). The molecular structure of [Pd{kappa(2)-(C6H3-OC6H13-4)-N=N-(C6H4-OC6H13-4 {kappa(2)-Ph2P(S)N(CHMe2)PPh2}](PF6) (15) has been determined by X-ray diffraction; the palladium bound carbon atom occupies the trans position with respect to the sulphur atom of the chelated diphosphazane monosulphide ligand