000127877 001__ 127877
000127877 005__ 20231023120953.0
000127877 0247_ $$2doi$$a10.1021/acs.organomet.9b00078
000127877 0248_ $$2sideral$$a112456
000127877 037__ $$aART-2019-112456
000127877 041__ $$aeng
000127877 100__ $$aAngoy, Marta
000127877 245__ $$aDinuclear Phosphine-Amido [Rh 2 (diene){µ-NH(CH 2 ) 3 PPh 2 } 2 ] Complexes as Efficient Catalyst Precursors for Phenylacetylene Polymerization
000127877 260__ $$c2019
000127877 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127877 5203_ $$aDinuclear 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.
000127877 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000127877 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000127877 590__ $$a3.804$$b2019
000127877 591__ $$aCHEMISTRY, ORGANIC$$b12 / 57 = 0.211$$c2019$$dQ1$$eT1
000127877 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b6 / 45 = 0.133$$c2019$$dQ1$$eT1
000127877 592__ $$a1.345$$b2019
000127877 593__ $$aInorganic Chemistry$$c2019$$dQ1
000127877 593__ $$aPhysical and Theoretical Chemistry$$c2019$$dQ1
000127877 593__ $$aOrganic Chemistry$$c2019$$dQ1
000127877 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000127877 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.Victoria$$uUniversidad de Zaragoza
000127877 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar$$uUniversidad de Zaragoza
000127877 700__ $$0(orcid)0000-0001-7154-7239$$aOro, Luis A.$$uUniversidad de Zaragoza
000127877 700__ $$0(orcid)0000-0002-4921-4734$$aVispe, Eugenio
000127877 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000127877 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127877 773__ $$g38, 9 (2019), 1991-2006$$pOrganometallics$$tOrganometallics$$x0276-7333
000127877 8564_ $$s1090865$$uhttps://zaguan.unizar.es/record/127877/files/texto_completo.pdf$$yPostprint
000127877 8564_ $$s2965889$$uhttps://zaguan.unizar.es/record/127877/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000127877 909CO $$ooai:zaguan.unizar.es:127877$$particulos$$pdriver
000127877 951__ $$a2023-10-23-11:03:04
000127877 980__ $$aARTICLE