Polystyrenes arene complex

The ability of n-arene metal complexes to coordinate additional metal atoms may be significant in the early stages of metallization of some phenyl-rich polymers. At the lowest coverages of say chromium on polystyrene, (arene)2Cr may be formed. With continued accumulation of metal these compounds may rapidly convert to thermally unstable organometallic cluster species that eventually expel the metal core. 

Fig. 12. Polystyrene anchored arene-chromium carbonyl complex...

Reaction of the arene ruthenium precursor 200 with polystyrene and hydrogen leads to the loss of both cycloolefins and gives a polymeric ruthenium complex, used for catalytic hydrogenation, for which EXAFS indicated a Ru—C distance of 2.05 A. A similar reaction of derivative 200 with 1,3-diphenylpropane gives complex 203 and a compound of composition (diphenylpropane)Ru2 (204) (129,130) [Eq. (18)]. 

In the first part of this article, focusing attention on polymer-supported cobalt phosphine complex 1 and arene ruthenium complex 2, we review contributions from our laboratory that show how organometallics can be efficiently attached to derivitised polystyrene and we outline their synthetic versatility.2,3 Following this, we discuss the preparation of a supported ruthenium complex, 3, and its use in oxidation and transfer hydrogenation catalysis. 

Polymers containing aryl groups also react efBdently with metal atoms to yield bis(arene)metal(0) complexes within the polymer chain . Thus, poly(methylphenyl-siloxanes) react at 0°C as a liquid with Ti, V, Cr, Mo and W atoms to give high yields of colored bis( / -arene)metal complexes. In contrast Co, Fe and Ni atoms )deld only metal slurries. Similarly, poly(oxyphenylene) and polystyrene (in a solvent) react with V and Cr atoms to yield colored solutions . By adjusting the metal-atom flux, small, polymer-supported Ti and Mo clusters can be prepared . In some cases the com-plexed metal atoms spontaneously migrate through the polymer fluid to form dimers . 

Recently, block copolymers micelles filled with MoS nanoparticles (well miscible with mineral oil) were synthesized in heptane using interaction of Mo(CO)e with polystyrene-fc/ock-polybutadiene (PS-fc-PB) and polystyrene-i /ock-polyisobutylene (PS-fc-PIB) followed by H2S treatment [39]. To position MoS c nanoparticles in the PS core, the reaction between Mo(CO)e and block copolymer should be carried out in argon atmosphere. This yields arene Mo tricarbonyl complexes while olefin Mo carbonyl complexes do not form. By contrast, to place MoS nanoparticles in the PB corona, complexation with Mo(CO)e should be carried out in the CO atmosphere. This suppresses forma-... 

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