The mono- and dinuclear rhodium(I) complexes featuring 2-(diphenylphosphino)pyridine ligands, [Rh(cod)(Ph2PPy)]+ and [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}]+, featuring a 2-(2-(diphenylphosphino)ethyl)pyridine ligand, that showed a moderate catalytic activity, both [Rh(diene)(Ph2PPy)]nn+ (n = 1, cod; n = 2, nbd) complexes showed no catalytic activity due to the formation of unusual dinuclear species [Rh2(diene)2(μ-Ph2PPy)(μ-C≡C-R)]+, supported by a Ph2PPy bridging ligand and an alkynyl ligand coordinated in a μ-η1:η2 fashion, which are inactive in PA polymerization. However, compounds [Rh(diene)(Ph2PPy)]nn+ efficiently polymerize PA in the presence of a cocatalyst as iPrNH2 affording highly stereoregular poly(phenylacetylene) (PPA) of Mw = 3.42 × 105 (cod) and 2.02 × 105 (nbd) with polydispersities of 1.39 and initiation efficiencies of 4–7%. NMR studies on the polymerization reaction have allowed identification of the alkynyl species [Rh(C≡CPh)(cod)(Ph2PPy)] as the likely initiating species involved in the generation of the rhodium-vinyl species responsible for the propagation step. The iPrNH2 cocatalyst is possibly involved in the efficient proton transfer from the coordinated PA to iPrNH2 that allows for a significant concentration of the key initiating species [Rh(C≡CPh)(cod)(Ph2PPy)]. The distinct behavior of compounds [Rh(diene)(Ph2PPy)]nn+ as PA polymerization catalysts is a consequence of the binucleating ability of the Ph2PPy ligand in combination with the low basicity of the pyridine fragment which allows for the stabilization of the inactive alkynyl-bridge dinuclear species.

Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) under the Project CTQ2016-75884-P and the Diputación General de Aragón (DGA/FSE-E07) is gratefully acknowledged.

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