Cluster-containing polymers as precursors of metal nanocomposites
Svetlana I. Pomogailo, Gulzhian I. Dzhardimalieva, Anatolii D.
Institute of Problems of Chemical Physics Russian Academy of Sciences,
Chernogolovka Moscow Region, 142432, Russia, E-mail: email@example.com
Cluster-containing polymers are obtained in two ways: by
immobilization of cluster compounds on macroligands, or by
copolymerization reactions of cluster-containing monomers
(m-H)Os(m-OCNM)(CO)PPHCHCH=CH) with traditional
vinyl monomers. It was found that Rh- and Os-containing monomers
did not change either the ligand surroundings or the structure of
cluster monomer framework during polymerization reaction. The
molecular weight parameters of the obtained copolymers were studied.
The catalytic properties of polymer-immobilized Rh- and Os
clusters obtained were studied in varied reactions. Rh-containing
polymers showed a high catalytic activity in hydrogenation of
cyclohexene, they can be used repeatedly without deactivation.
Carbonylation of methanol in protonic medium proceeded effectively in
the presence of Os copolymer with styrene and resulted in formation
of formic acid and trifluoroacetate. These polymer clusters were also
efficient in hydrogenation of styrene under supercritical CO. The
catalytic hydroxylation of olefins by organic hydroperoxides in the
presence of osmium-containing polymers were studied. It was shown
that reaction proceeded with preferred formation of unsaturated
alcohols. Oxidative dimerisation of olefins into nonconjugated dienes
were also observed. The influence of nature of ligands and polymer
matrix as well as a specific content of metal on catalytic activity
and composition of products formed are discussed.