Polymers metal-backbone organometallic

As surmized in a recent review article there are literally hundreds of polymeric systems featuring organometallic complexes within a conjugated organic backbone. Given recent reviews of these systems, here we shall restrict discussion to the various polymeric species and ceramic materials derived from diyne complexes and from coordination of metal fragments to polymers featuring C=CC=C repeat units. 

Another application of hyperbranched polymers as supports for catalysts is their use as backbones for the covalent attachment of organometallic fragments. NCN-pincer complexes (NCN-pincer = 2,6-bis[(dimethylamino)-methyl] phenyl anion) are attractive building blocks for catalytic reactions [20,21], Covalent introduction of the transition-metal complexes can also be of interest for visualization and imaging of dendritic polymers by transmission electron microscopy (TEM). 

Examples of organometallic polymers containing both phosphorus atoms and transition metals in the backbone include polyferrocenylphosphines 8 (and the corresponding phosphine sulfides 9), which are accessible via the thermal ROP of phosphorus-bridged [1] ferrocenophanes [16,17]. Polymers of this type have been previously prepared by condensation routes and the catalytic potential of some of their transition metal derivatives has already been noted [18]. Living anionic ROP of phosphorus-bridged [l]ferrocenophanes has recently been demonstrated and provides a route to block copolymers such as 10 (PI = poly-isoprene) [19] ... 

The research area of organometallic polymers containing transition metals cr-bonded in the polymer backbone is dominated by poly(metal acetylides).34,35 Since their discovery in the 1970s,... 

As with other polymers, the metal complex may be part of the polymer backbone, or attached to the backbone by a conjugated linker. Investigations into the conjugated polymers have been assisted by studies of model complexes.44 Polythiophenes incorporating organometallic complexes are discussed first, followed by those incorporating other coordination complexes with bipyridine, terpyridine, Schiff base, and other ligands. 

In 2001, an efficient step-growth polycondensation approach, reminiscent of that used to prepare metal-metal-bonded polymers 217 and 218, was successfully developed to yield polyurethanes 225 with Mo2lt2 clusters in the backbone. " Well-characterized polymers with molecular weights of up to 136,000 (PDI = 3.1), which correspond to a number average of around 30 clusters per polymer chain, were obtained by means of this method. It involved treatment of a diol of the Mo2lt2 cluster with the diisocyanate OCN-R-NGO (R = aliphatic or aromatic spacer) in the presence of a tin catalyst. The unusual optical properties of organometallic clusters will drive applications-oriented work on these materials. " ... 

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