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Título

Dinuclear phosphine-amido [Rh2(diene){μ-NH(CH2)3PPh2}2] complexes as efficient catalyst precursors for phenylacetylene polymerization

AutorAngoy, Marta CSIC; Jiménez, M. Victoria CSIC ORCID ; García-Orduña, Pilar CSIC ORCID; Oro, Luis A. CSIC ORCID; Vispe, Eugenio CSIC ORCID; Pérez-Torrente, Jesús J. CSIC ORCID
Fecha de publicación13-may-2019
EditorAmerican Chemical Society
CitaciónOrganometallics 38(9): 1991-2006 (2019)
ResumenDinuclear phosphine-amido, [Rh(diene){μ-NH(CH)PPh}], and cationic phosphine-amino complexes, [Rh(diene){PhP(CH)NHR}] (diene = cod, nbd, tfb) and [Rh{PhP(CH)NHR}], have been prepared from the corresponding amino-functionalized phosphines PhP(CH)NHR (R = H, Me) and suitable rhodium(I) precursors. The dinuclear [Rh(diene){μ-NH(CH)PPh}] complexes bearing π-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 up to ≈ 1.2 × 10, and moderate polydispersity indexes. These complexes are more active than the mononuclear phosphino-anilido [Rh(diene){PhP(CH)NMe}] complexes, which are in turn more active than the cationic complexes [Rh(diene){PhP(CH)NHMe}], [Rh(nbd){PhP(CH)NH}], and [Rh(nbd){PhP(CH)NHMe}] bearing the same diene ligand. In contrast, complexes [Rh{PhP(CH)NHR}] (R = H, Me) without a diene ligand have been found to be inactive in PA polymerization. The excellent catalytic performance of [Rh(diene){μ-NH(CH)PPh}] (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.
Versión del editorhttp://doi.org/10.1021/acs.organomet.9b00078
URIhttp://hdl.handle.net/10261/208618
DOI10.1021/acs.organomet.9b00078
Identificadoresdoi: 10.1021/acs.organomet.9b00078
e-issn: 1520-6041
issn: 0276-7333
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