Synthesis and properties of Rh6- and Os3-cluster-containing monomers and their copolymers with styrene

Cluster metal-containing monomers were obtained and characterized. Mono- and disubstituted products were obtained under mild conditions via the interaction of Rh₆(CO)₁₆ with 4-vinylpyridine (4-VPy) in the presence of trimethylamin-N-oxide. Substitution of labile acetonitrile ligand in Rh₆(CO)₁₅NCMe by allyldiphenylphosphine (AlPPh₂) yields Rh₆(CO)₁₄(μ,η²-PPh₂CH₂CH=CH₂) with formation of π-complex. The structures of Rh₆(CO)₁₅(4-VPy), Rh₆(CO)₁₄(μ,η²-PPh₂CH₂CH=CH₂) and (μ-H)Os₃(μ-OCNM₂)(CO)₉PPH₂CH₂CH=CH₂ have been determined by single-crystal X-ray diffraction studies, as well as by IR-, ¹H NMR spectroscopies. The Rh - Rh bond lengths are within 2.72÷2.80 Å. The copolymerization of cluster-containing monomers synthesized with traditional monomers has been studied. It was found that Rh₆- and Os₃-containing monomers did not change either the ligand surroundings or the structure of cluster monomer framework during polymerization reaction.