doi:10.1021/acs.organomet.9b00078engAngoy, MartaJiménez, M.VictoriaGarcía-Orduña, PilarOro, Luis A.Vispe, EugenioPérez-Torrente, Jesús J.Dinuclear Phosphine-Amido [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ] Complexes as Efficient Catalyst Precursors for Phenylacetylene PolymerizationART-2019-112456Dinuclear phosphine-amido, [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ], and cationic phosphine-amino complexes, [Rh(diene){Ph 2 P(CH 2 ) 3 NHR}] + (diene = cod, nbd, tfb) and [Rh{Ph 2 P(CH 2 ) 3 NHR} 2 ] + , have been prepared from the corresponding amino-functionalized phosphines Ph 2 P(CH 2 ) 3 NHR (R = H, Me) and suitable rhodium(I) precursors. The dinuclear [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ] complexes bearing p-acceptors diene ligands such as nbd or tfb exhibit a remarkable catalytic activity in phenylacetylene (PA) polymerization affording stereoregular polyphenylacetylenes with, unlike the cod precursor, unimodal molar mass distributions of very high molecular weights, M w up to ˜ 1.2 × 10 6 , and moderate polydispersity indexes. These complexes are more active than the mononuclear phosphino-anilido [Rh(diene){Ph 2 P(C 6 H 4 )NMe}] complexes, which are in turn more active than the cationic complexes [Rh(diene){Ph 2 P(CH 2 ) 3 NHMe}] + , [Rh(nbd){Ph 2 P(CH 2 ) 3 NH 2 }] + , and [Rh(nbd){Ph 2 P(C 6 H 4 )NHMe}] + bearing the same diene ligand. In contrast, complexes [Rh{Ph 2 P(CH 2 ) 3 NHR} 2 ] + (R = H, Me) without a diene ligand have been found to be inactive in PA polymerization. The excellent catalytic performance of [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ] (diene = nbd, tfb) complexes is a consequence of the mode of activation of PA that likely results in the formation of unsaturated alkynyl species [Rh(diene)(CC-Ph)L] (L = PA, THF), which may be competent for PA polymerization. © 2019 American Chemical Society.2019http://zaguan.unizar.es/record/12787710.1021/acs.organomet.9b00078http://zaguan.unizar.es/record/127877oai:zaguan.unizar.es:127877info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17Rinfo:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-Pinfo:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-POrganometallics 38, 9 (2019), 1991-2006All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess