Cyclopalladated hydrazones complexed to pyridinyl ligands

2-Benzoylpyridine and 2-acetylpyridine N-methyl-N-phenylhydrazones (HL1 and HL2) in cyclopalladation reactions with Pd3(OAc)6 behave as N(py)N(im)C tridentate ligands and form the neutral mononuclear complexes [Pd(k3-N,N,C–L1,2)(k1-OAc)] (1 and 2). The labile OAc ligand can be replaced by pyridine (py) and, in the presence of NH4PF6, a compound of the general formula [Pd(k3-N,N,C-L1,2)(py)]PF6 (3 and 4) can be obtained. Reacting 1 or 2 with the poly(4-vinylpyridine) polymer (PVP, image) adducts of the general formula x[Pd(k3-N,N,C-L1,2)(PF6)] · y[PVP] gives (5a–c and 6a–c, a–c: x/y = 80/20, 50/50, 25/75 w/w) containing the laterally appended cyclopalladated “Pd(k3-N,N,C-L1,2)” fragments. These metallorganic polymers show high glass transition temperatures, high thermal stability and good solubility, and are optimal for obtaining transparent thin films by the spin coating method.