127877 20231023120953.0 doi 10.1021/acs.organomet.9b00078 sideral 112456 ART-2019-112456 eng Angoy, Marta Dinuclear Phosphine-Amido [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ] Complexes as Efficient Catalyst Precursors for Phenylacetylene Polymerization 2019 Dinuclear 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. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 3.804 2019 CHEMISTRY, ORGANIC 12 / 57 = 0.211 2019 Q1 T1 CHEMISTRY, INORGANIC & NUCLEAR 6 / 45 = 0.133 2019 Q1 T1 1.345 2019 Inorganic Chemistry 2019 Q1 Physical and Theoretical Chemistry 2019 Q1 Organic Chemistry 2019 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Jiménez, M.Victoria Universidad de Zaragoza (orcid)0000-0002-0545-9107 García-Orduña, Pilar Universidad de Zaragoza (orcid)0000-0002-7063-1292 Oro, Luis A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Vispe, Eugenio (orcid)0000-0002-4921-4734 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 38, 9 (2019), 1991-2006 Organometallics Organometallics 0276-7333 1090865 http://zaguan.unizar.es/record/127877/files/texto_completo.pdf Postprint 2965889 http://zaguan.unizar.es/record/127877/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:127877 articulos driver 2023-10-23-11:03:04 ARTICLE