Rhodium(I)-a-Phenylvinylfluorenyl Complexes: Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene

Tan, N. and Simpson, P. and Nealon, G. and Sobolev, A. and Raiteri, P. and Massi, M. and Ogden, M. et al. 2019. Rhodium(I)-a-Phenylvinylfluorenyl Complexes: Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene. European Journal of Inorganic Chemistry. 2019 (5): pp. 592-601.

Source Title

European Journal of Inorganic Chemistry

DOI

10.1002/ejic.201801411

ISSN

1434-1948

School

Nanochemistry Research Institute

URI

http://hdl.handle.net/20.500.11937/74718

Collection

Curtin Research Publications

Abstract

The synthesis, characterization and use, as initiators for phenylacetylene polymerizations, of three new rhodium(I)-vinyl complexes containing fluorenyl functionality with fluorine-functionalized phosphine ligands is described. Rh(nbd)(CPh=CFlu)P(4-FC6H4)3, Rh(nbd)(CPh=CFlu)P(4-CF3C6H4)3, and Rh(nbd)(CPh=CFlu)P[3,5-(CF3)2C6H3]3 (nbd: 2,5-norbornadiene; Flu: fluorenyl) were prepared and isolated as discrete, orange compounds and were readily recrystallized yielding X-ray quality crystals. All complexes were characterized by a combination of 1H, 31P, 19F, 103Rh NMR spectroscopy and 2D 31P-103Rh/31P-103Rh{103Rh} heteronuclear multiple-quantum correlation (HMQC) experiments, elemental analysis, and single-crystal X-ray analysis. The complexes were active as initiators in the co-ordination insertion polymerization of phenylacetylene, with initiation efficiencies spanning the range 13–56 %, and yielded polyphenylacetylenes of low dispersity (Ð = Mw/Mn) with high cis-transoidal stereoregularity.