Y. Kishimoto, P. Eckerle, Tatsuya Miyatake
Dec 10, 1999
Citations
3
Influential Citations
180
Citations
Quality indicators
Journal
Journal of the American Chemical Society
Abstract
A tetracoordinate rhodium complex, Rh(C⋮CC6H5)(nbd)[P(C6H5)3] (nbd = 2,5-norbornadiene), combined with 4-(dimethylamino)pyridine (DMAP) is an excellent initiator for the stereospecific living polymerization of phenylacetylene and its m- and p-substituted derivatives. The rhodium initiator can be generated efficiently by dissociation of triphenylphosphine from isolable Rh(C⋮CC6H5)(nbd)[P(C6H5)3]2 or by reacting Rh(CH3)(nbd)[P(C6H5)3]2 or [Rh(OCH3)(nbd)]2/P(C6H5)3 with one equivalent of phenylacetylene. The use of a phenylethynyl group, triphenylphosphine, and NBD ligand attached to the rhodium center is crucial for the well-controlled polymerization of phenylacetylenes. An additive, DMAP, is necessary to attain low polydispersities of the polymer products. An active rhodium(I) complex bearing a growing polymer chain, NBD, and P(C6H5)3 was isolated from a reaction mixture and was characterized by NMR, GC−MS, XPS, and elemental analyses. The isolated active polymer initiates the further polymerization of the...