Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s

Funding: We gratefully acknowledge financial support from the Ministerio de Ciencia, Innovación y Universidades, Spain (grant nos. CTQ2017-84131-R, RED2018-102387-T and PID2020-117788RB-I00).

Detalles Bibliográficos
Autores: Navarro, Marta, Garcés, Andrés, Sánchez-Barba, Luis Fernando, de la Cruz-Martínez, Felipe, Fernández-Baeza, Juan, Lara-Sánchez, Agustín
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universidad Rey Juan Carlos
Repositorio:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
OAI Identifier:oai:burjcdigital.urjc.es:10115/30554
Acceso en línea:https://hdl.handle.net/10115/30554
Access Level:acceso abierto
Palabra clave:homogenous catalysis
zinc scorpionates
rac-lactide
heterotactic poly(rac-lactide)s
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spelling Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)sNavarro, MartaGarcés, AndrésSánchez-Barba, Luis Fernandode la Cruz-Martínez, FelipeFernández-Baeza, JuanLara-Sánchez, Agustínhomogenous catalysiszinc scorpionatesrac-lactideheterotactic poly(rac-lactide)sFunding: We gratefully acknowledge financial support from the Ministerio de Ciencia, Innovación y Universidades, Spain (grant nos. CTQ2017-84131-R, RED2018-102387-T and PID2020-117788RB-I00).The direct reaction of the highly sterically demanding acetamidinate-based NNN-scorpionate protioligand Hphbptamd [Hphbptamd = N,N0-di-p-tolylbis(3,5-di-tertbutylpyrazole-1-yl)acetamidine] with one equiv. of ZnMe2 proceeds in high yield to the mononuclear alkyl zinc complex [ZnMe(k3-phbptamd)] (1). Alternatively, the treatment of the corresponding lithium precursor [Li(phbptamd) (THF)] with ZnCl2 yielded the halide complex [ZnCl(k3-phbptamd)] (2). The X-ray crystal structure of 1 confirmed unambiguously a mononuclear entity in these complexes, with the zinc centre arranged with a pseudotetrahedral environment and the scorpionate ligand in a k3-coordination mode. Interestingly, the inexpensive, low-toxic and easily prepared complexes 1 and 2 resulted in highly efficient catalysts for the ring-opening polymerisation of lactides, a sustainable bio-resourced process industrially demanded. Thus, complex 1 behaved as a single-component robust initiator for the living and immortal ROP of rac-lactide under very mild conditions after a few hours, reaching a TOF value up to 5520 h1 under bulk conditions. Preliminary kinetic studies revealed apparent zero-order dependence on monomer concentration in the absence of a cocatalyst. The PLA materials produced exhibited narrow dispersity values, good agreement between the experimental Mn values and monomer/benzyl alcohol ratios, as well as enhanced levels of heteroselectivity, reaching Ps values up to 0.74.MDPI202420242021info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/10115/30554reponame:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlosinstname:Universidad Rey Juan CarlosInglésAttribution 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:burjcdigital.urjc.es:10115/305542026-06-24T12:48:17Z
dc.title.none.fl_str_mv Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
title Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
spellingShingle Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
Navarro, Marta
homogenous catalysis
zinc scorpionates
rac-lactide
heterotactic poly(rac-lactide)s
title_short Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
title_full Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
title_fullStr Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
title_full_unstemmed Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
title_sort Efficient Bulky Organo-Zinc Scorpionates for the Stereoselective Production of Poly(rac-lactide)s
dc.creator.none.fl_str_mv Navarro, Marta
Garcés, Andrés
Sánchez-Barba, Luis Fernando
de la Cruz-Martínez, Felipe
Fernández-Baeza, Juan
Lara-Sánchez, Agustín
author Navarro, Marta
author_facet Navarro, Marta
Garcés, Andrés
Sánchez-Barba, Luis Fernando
de la Cruz-Martínez, Felipe
Fernández-Baeza, Juan
Lara-Sánchez, Agustín
author_role author
author2 Garcés, Andrés
Sánchez-Barba, Luis Fernando
de la Cruz-Martínez, Felipe
Fernández-Baeza, Juan
Lara-Sánchez, Agustín
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv homogenous catalysis
zinc scorpionates
rac-lactide
heterotactic poly(rac-lactide)s
topic homogenous catalysis
zinc scorpionates
rac-lactide
heterotactic poly(rac-lactide)s
description Funding: We gratefully acknowledge financial support from the Ministerio de Ciencia, Innovación y Universidades, Spain (grant nos. CTQ2017-84131-R, RED2018-102387-T and PID2020-117788RB-I00).
publishDate 2021
dc.date.none.fl_str_mv 2021
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10115/30554
url https://hdl.handle.net/10115/30554
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv Attribution 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution 4.0 Internacional
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
instname:Universidad Rey Juan Carlos
instname_str Universidad Rey Juan Carlos
reponame_str BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
collection BURJC-Digital. Repositorio Institucional de la Universidad Rey Juan Carlos
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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