Development of new polymeric materials via coupling of mechanistically incompatible reactions using Ru/Pd and Ru/Ni heterobimetallic catalysts

• Grant number: 21/13128-1
• Support Opportunities: Regular Research Grants
• Start date: July 01, 2022
• End date: July 31, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Valdemiro Pereira de Carvalho Júnior
• Grantee: Valdemiro Pereira de Carvalho Júnior
• Host Institution: Faculdade de Ciências e Tecnologia (FCT). Universidade Estadual Paulista (UNESP). Campus de Presidente Prudente. Presidente Prudente , SP, Brazil
• Associated researchers: André Luiz Bogado ; Beatriz Eleutério Goi Carvalho ; Katia Bernardo Gusmão

Abstract

The coupling of mechanistically distinct reactions different, ethylene polymerization, ring opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) simultaneously will be mediated by new heterobimetallic complexes of RuII/PdII and RuII/NiII. The proposal is to systematically evaluate different combinations of ancillary ligands in the coordination sphere of heterobimetallic complexes and then, reach a fine-tuning through the variation of the electronic and steric contributions in both metal center. Thus, the reactivity of each metallic center can be adjusted in order to direct the reactivity of these complexes to act efficiently in the double coupling: ROMP/ATRP and ethylene polymerization/ROMP, and then, in the triple coupling: ethylene polymerization/ROMP/ATRP. Initially, the research will focus on the catalytic activity of the complexes in these reactions separately, considering that a wide understanding of individual reactions will be a key step towards to the development of multifunctional catalysts for tandem catalysis of these reactions. The idea is to provide knowledge for understanding the performance of the catalysts, as well as the formation of reaction intermediates involved in each reaction, and then, design multifunctional catalytic systems that combine reactivity and selectivity for synthesis of new materials with different architecture by tandem polymerization; these efforts are aimed at transferring technology. (AU)

Scientific publications

(6)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

CICERO MASSON, GUSTAVO HENRIQUE; BALLICO, MAURIZIO; GOI, BEATRIZ ELEUTERIO; DE CARVALHO, VALDEMIRO PEREIRA; BARATTA, WALTER. Light-enhancing ketone transfer hydrogenation catalyzed by diphosphine phenanthroline ruthenium complexes. MOLECULAR CATALYSIS, v. 564, p. 11-pg., 2024-06-27. (21/13128-1, 21/11873-1)

SANTOS, DOUGLAS H. N.; MASSON, GUSTAVO H. C.; SILVA, ELIADA A.; RUBIRA, RAFAEL J. G.; NASCIMENTO, OTACIRO R.; BERNARDO-GUSMAO, KATIA; LIMA-NETO, BENEDITO S.; GOI, BEATRIZ E.; CARVALHO-JR, VALDEMIRO P.. Tandem ROMP/Vinyl-Addition Polymerization of Norbornene Catalyzed by a Ru/Ni Heterobimetallic Complex. JOURNAL OF POLYMER SCIENCE, v. N/A, p. 12-pg., 2025-03-29. (22/12417-2, 21/13128-1, 21/11873-1)

FIGUEIREDO, MARIA L. B.; BIGNARDI, CAMILA; PESQUEIRA, NARALYNE M.; MACHADO, ANTONIO E. H.; CARVALHO-JR, VALDEMIRO P.; NASCIMENTO, OTACIRO R.; GOI, BEATRIZ E.. Well-defined non-symmetric NHC-iron(III) catalyst for photoinduced atom-transfer radical polymerization of methyl methacrylate. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 452, p. 8-pg., 2024-03-08. (21/13128-1, 22/16571-6, 21/11873-1)

PESQUEIRA, NARALYNE M.; LIRA, KATHIA H.; BIGNARDI, CAMILA; DA SILVA, MILENE K. C.; SILVA, THIAGO F.; MACHADO, ANTONIO E. H.; NASCIMENTO, OTACIRO R.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Photo-induced organo-manganese-mediated radical polymerization of acrylates under LED irradiation. APPLIED ORGANOMETALLIC CHEMISTRY, v. 38, n. 7, p. 14-pg., 2024-04-28. (21/13128-1, 22/16571-6, 21/11741-8, 21/11873-1)

PESQUEIRA, NARALYNE M.; MORLET-SAVARY, FABRICE; SCHMITT, MICHAEL; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.; LALEVEE, JACQUES. Advancing photopolymerization and 3D printing: High-Performance Ni II complexes bearing N 2 O 2 Schiff-base ligands as photocatalysts. EUROPEAN POLYMER JOURNAL, v. 216, p. 13-pg., 2024-07-03. (21/13128-1, 21/11873-1, 21/11741-8, 22/16213-2)

CRUZ, THAIS R.; MASSON, GUSTAVO H. C.; AMORIM, KELLY A. E.; MACHADO, ANTONIO E. H.; GOI, BEATRIZ E.; CARVALHO-JR, VALDEMIRO P.. Ru/Pd Complex and Its Monometallic Fragments as Catalysts for Norbornene Polymerization via ROMP and Addition. CATALYSTS, v. 12, n. 10, p. 16-pg., 2022-10-01. (21/13128-1, 18/06340-1, 21/11873-1)