The structures of the precipitates of free‐radical poly(4‐vinylpyridine) (Vpy), free‐radical poly(2‐Vpy) and isotactic poly(2‐Vpy) with M(II)Cl2 (M = Co, Ni, Cu, Zn) obtained from solution have been investigated. The polymer compounds are similar to the known crystalline monomeric Vpy complexes and, with one exception, are crosslinked by the metal dichloride. Co(II) and Zn(II) are tetrahedrally coordinated by the polymer, while the Ni(II) and Cu(II) complexes are probably tetrahedral and square‐planar, respectively. Because of the constraints of the polymeric ligands the stoichiometries of the complexes are not exactly the same as those of the monomeric Vpy complexes and from one to two Vpy units per metal halide are on average not coordinated. Atactic and isotactic poly(2‐Vpy) showed marked differences with regard to coordination of Ni(II). The questions of stereochemistry of the coordinated metal ion, stoichiometry of the complexes, intermolecular versus intramolecular complexation of the polymer chain, and the influence of polymer tacticity on the crystallizability of polymer complexes are discussed.

No abstract

No abstract

No abstract

No abstract