In the last fifteen years, a large variety of specialty polymers of diverse chemical structure and functionality have been synthesized with the rhodium-based catalysts. The high tolerance to the reaction medium and functional groups of monomers, as well as ability to control various structure features of the polymer formed are typical properties of these catalysts. In addition, some rhodium catalysts can be anchored to inorganic or organic supports or dissolved in ionic liquids to form heterophase polymerization systems, which opens the way to pure, well-defined polymers free of the catalyst residues, as well as to recycling rhodium catalysts. This review provides a survey on the polymerization reactions induced with rhodium-based catalysts, in which one or more structure attributes of the polymer formed are subject to control. The structure attributes considered are (i) sequential arrangement of monomeric units along polymer chains; (ii) head-tail isomerism of polymer molecules; (iii) configurational structure of polymer molecules; (iv) conformation of polymer molecules; and (v) molecular weight and molecular-weight distribution of the polymer formed. A review with 188 references.

The Rh based catalysts are efficient and versatile tool for the polymerization of monomers containing terminal ethynyl group(s) in the molecule. They exhibit high tolerance to the reaction medium and monomer functional groups and produce polyacetylenes of high microstructure uniformity. Main types of Rh based catalysts including those immobilized on both organic and siliceous supports were reviewed. The following architecture types of polyacetylenes are feasible using these catalysts: (i) linear polyacetylenes with pendants of various functionality and bulkiness, (ii) branched polyacetylenes, and (iii) highly cross-linked polyacetylene networks. The networks prepared from diethynylarenes exhibit microporous/mesoporous texture and considerable gas adsorption capacities.