Mechanistic Investigation on the Polymerization of Phenylacetylene by 2-Diphenylphosphinopyridine Rhodium(I) Catalysts: Understanding the Role of the Cocatalyst and Alkynyl Intermediates
作者： Marta Angoy , M. Victoria Jiménez , F. Javier Modrego , Luis A. Oro , Vincenzo Passarelli
DOI: 10.1021/ACS.ORGANOMET.8B00430
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摘要: The mono- and dinuclear rhodium(I) complexes featuring 2-(diphenylphosphino)pyridine ligands, [Rh(cod)(Ph2PPy)]+ [Rh(nbd)(μ-Ph2PPy)]22+ (cod = 1,5-cyclooctadiene, nbd 2,5-norbornadiene), have been prepared in order to be evaluated as phenylacetylene (PA) polymerization catalysts. In contrast with compound [Rh(nbd){Ph2P(CH2)2Py}]+, a 2-(2-(diphenylphosphino)ethyl)pyridine ligand, that showed moderate catalytic activity, both [Rh(diene)(Ph2PPy)]nn+ (n 1, cod; n 2, nbd) no activity due the formation of unusual species [Rh2(diene)2(μ-Ph2PPy)(μ-C≡C-R)]+, supported by Ph2PPy bridging ligand an alkynyl coordinated μ-η1:η2 fashion, which are inactive PA polymerization. However, compounds efficiently polymerize presence cocatalyst iPrNH2 affording highly stereoregular poly(phenylacetylene) (PPA) Mw 3.42 × 105 (cod) 2.02 (nbd) polydispersities 1.39 initiation efficie...
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