Coordination crosslinks poly

Other results reported concern the reactivity of Fe(II)porphyrin attached to the surface of a solid. Collman et al.99) prepared Fe(II)(TPP) 39 coordinated to an imidazole group bonded to crosslinked poly(styrene), as represented in 40. Treatment of 40 with oxygen in benzene caused oxidation and formed the n-oxo dimer... 

It should be noted extra-coordination processes are also important in controlling the properties of metallopolymers. Thus mechanical parameters and performance of many metal-containing polymers are determined by the ability of the metals to form ionic or coordination crosslinks (i.e., additional interchain interaction), and to exhibit cohesion and adhesion properties. Formally, unit variability in these cases is determined by the presence of metals in the chain with different coordination numbers. The incorporation of cluster-containing Os3-monomers into a polystyrene or poly(acrylonitrile) chain results in a mutual thermal stabilization of both the polymers and the clusters incorporated into the chains. These effects are observed only in cases where the cluster monomers are chemically bound to the polymeric chain. The influence of the chain may be manifested as the transfer of energy from the rotation-vibration degrees of freedom of the cluster to the translational degrees of freedom of the polymer chain segments at elevated temperatures. 

Wright examined the synthesis of different classes of chromium tricarbonyl-coordinated polymers. Poly(phenyl ethynyl)s coordinated to chromium tricarbonyl moieties (21, 23) were synthesized by palladium catalyzed cross-coupling of (r -l,4-dichloroarene)tricarbonyl chromium complexes with organostannane reagents (Scheme 4). ° Combustion analysis of these polymers indicated that their degree of polymerization was 18, which corresponds to a MW of 7800. Combustion and IR analysis of polymers that were heated above 200°C indicated that crosslinking reactions occurred followed by loss of carbon monoxide from the Cr(CO)3 moieties. 

Synthetic polymers with side chains that can form coordination complexes, such as polycarboxylic acids, polyols and polyamines, will form crosslinks by adding multivalent metallic ions [39]. For example, when NH2 is added to a copper sul te solution of poly(vinyl alcohol), the polymer becomes insoluble [40]. 

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