000127879 001__ 127879
000127879 005__ 20231023120953.0
000127879 0247_ $$2doi$$a10.1021/acs.organomet.8b00430
000127879 0248_ $$2sideral$$a107933
000127879 037__ $$aART-2018-107933
000127879 041__ $$aeng
000127879 100__ $$aAngoy, M.
000127879 245__ $$aMechanistic Investigation on the Polymerization of Phenylacetylene by 2-Diphenylphosphinopyridine Rhodium(I) Catalysts: Understanding the Role of the Cocatalyst and Alkynyl Intermediates
000127879 260__ $$c2018
000127879 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127879 5203_ $$aThe mono- and dinuclear rhodium(I) complexes featuring 2-(diphenylphosphino)pyridine ligands, [Rh(cod)(Ph2PPy)(+) and [Rh(nbd)(mu-Ph2PPY)(2)(2+) (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)(2)Py}(+), featuring a 2 -(2-(diphenylphosphino)ethyl)pyridine ligand, that showed a moderate catalytic activity, both [Rh(diene)(Ph2PPy)](n)(n+) (n = 1, cod; n = 2, nbd) complexes showed no catalytic activity due to the formation of unusual dinuclear species [Rh-2(diene)(2)(mu-Ph2PPy)(mu-C=C-R))+, supported by a Ph2PPy bridging ligand and an alkynyl ligand coordinated in a mu-eta(1):eta(2) fashion, which are inactive in PA polymerization. However, compounds [Rh(diene)(Ph2PPy)](n)(n+) efficiently polymerize PA in the presence of a cocatalyst as iPrNH(2) affording highly stereoregular poly(phenylacetylene) (PPA) of My, = 3.42 X 10(5) (cod) and 2.02 X 10(5) (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 equivalent to CPh)(cod)(Ph2PPy)] as the likely initiating species involved in the generation of the rhodium-vinyl species responsible for the propagation step. The iPrNH(2) cocatalyst is possibly involved in the efficient proton transfer from the coordinated PA to iPrNH(2) that allows for a significant concentration of the key initiating species [Rh(C-CPh)(cod)(Ph2PPy)]. The distinct behavior of compounds [Rh(diene)(Ph2PPy)](n)(n+) 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.
000127879 536__ $$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000127879 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000127879 590__ $$a4.1$$b2018
000127879 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2018$$dQ1$$eT1
000127879 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 45 = 0.111$$c2018$$dQ1$$eT1
000127879 592__ $$a1.473$$b2018
000127879 593__ $$aInorganic Chemistry$$c2018$$dQ1
000127879 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000127879 593__ $$aOrganic Chemistry$$c2018$$dQ1
000127879 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000127879 700__ $$0(orcid)0000-0002-0545-9107$$aJimenez, M.V.$$uUniversidad de Zaragoza
000127879 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F.J.$$uUniversidad de Zaragoza
000127879 700__ $$0(orcid)0000-0001-7154-7239$$aOro, L.A.$$uUniversidad de Zaragoza
000127879 700__ $$aPassarelli, V.
000127879 700__ $$0(orcid)0000-0002-3327-0918$$aPerez-Torrente, J.J.$$uUniversidad de Zaragoza
000127879 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127879 773__ $$g37, 16 (2018), 2778-2794$$pOrganometallics$$tOrganometallics$$x0276-7333
000127879 8564_ $$s1267628$$uhttps://zaguan.unizar.es/record/127879/files/texto_completo.pdf$$yPostprint
000127879 8564_ $$s2967437$$uhttps://zaguan.unizar.es/record/127879/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000127879 909CO $$ooai:zaguan.unizar.es:127879$$particulos$$pdriver
000127879 951__ $$a2023-10-23-11:03:22
000127879 980__ $$aARTICLE