Bimetallic complexes of ruthenium(II) and nickel(II): coupling of mechanistically-incompatible reactions using multifunctional catalysts via tandem catalysis

• Grant number: 18/06340-1
• Support Opportunities: Regular Research Grants
• Start date: June 01, 2019
• End date: May 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic 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

Abstract

Heterobimetallic complexes of ruthenium(II) and nickel(II) will be synthesized to mediate the coupling of three mechanistically distinct reactions different: transition metal catalyzed ethylene polymerization, ring opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) simultaneously. 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, for the initiation and propagation rates in the polymerizations, for driving the reactivity of these complexes to operate efficiently in the tandem catalysis of transition metal catalyzed ethylene polymerization with ROMP and ATRP. Initially, the research will focus on the catalytic activity of the complexes in these three 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 transition metal catalyzed ethylene polymerization with ROMP and ATRP. 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

(15)

(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)

BIGNARDI, CAMILA; OLIVEIRA, LARISSA F.; PESQUEIRA, NARALYNE M.; RIGA-ROCHA, BEATRIZ A.; MACHADO, ANTONIO E. H.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Photoinduced organometallic mediating radical polymerization of acrylates mediated by CoII complexes of non-symmetrical tetradentate Schiff-base ligands. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 423, p. 9-pg., 2021-10-11. (18/06340-1, 18/19395-9)

OLIVEIRA, LARISSA F.; BIGNARDI, CAMILA; PESQUEIRA, NARALYNE M.; RIGA-ROCHA, BEATRIZ A.; MACHADO, ANTONIO E. H.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type Co-II complexes. EUROPEAN POLYMER JOURNAL, v. 159, OCT 5 2021. (18/06340-1, 19/03354-4, 18/19395-9)

MASSON, GUSTAVO H. C.; CRUZ, THAIS R.; GOIS, PATRIK D. S.; MARTINS, DANIELE M.; LIMA-NETO, BENEDITO S.; OLIVEIRA, GUEDMILLER S.; MACHADO, ANTONIO E. H.; BERNARDO-GUSMAO, KATIA; GOI, BEATRIZ E.; CARVALHO-JR, VALDEMIRO P.. Ruthenium-nickel heterobimetallic complex as a bifunctional catalyst for ROMP of norbornene and ethylene polymerization. NEW JOURNAL OF CHEMISTRY, v. 45, n. 26, p. 11466-11473, JUL 14 2021. (18/19395-9, 18/06340-1)

PESQUEIRA, NARALYNE M.; BIGNARDI, CAMILA; OLIVEIRA, LARISSA F.; MACHADO, ANTONIO E. H.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Visible light-induced radical polymerization of vinyl acetate mediated by organo-nickel N2O2 Schiff-base complexes. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 437, p. 11-pg., 2023-03-01. (18/19395-9, 21/11741-8, 18/06340-1)

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)

CRUZ, THAIS R.; SILVA, ELIADA A.; OLIVEIRA, DOUGLAS P.; MARTINS, DANIELE M.; GOIS, PATRIK D. S.; MACHADO, ANTONIO E. H.; MAIA, PEDRO IVO S.; GOI, BEATRIZ E.; LIMA-NETO, BENEDITO S.; CARVALHO-JR, VALDEMIRO P.. Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations. Applied Organometallic Chemistry, v. 34, n. 5, FEB 2020. (18/06340-1, 17/06329-5)

GOIS, PATRIK D. S.; CRUZ, THAIS R.; MARTINS, DANIELE M.; MACHADO, ANTONIO E. H.; BOGADO, ANDRE L.; LIMA-NETO, BENEDITO S.; GOI, BEATRIZ E.; CARVALHO JR, VALDEMIRO P.. Cyclic amines homobimetallic ruthenium pre-catalysts bearing bidentate phosphine and their dual catalytic activity for the ring-opening metathesis and atom-radical polymerizations. Journal of Molecular Structure, v. 1198, DEC 15 2019. (18/06340-1, 17/06329-5)

RIGA, BEATRIZ A.; SILVA, YAN F.; NASCIMENTO, OTACIRO R.; MACHADO, ANTONIO E. H.; CARVALHO, JR., VALDEMIRO P.; GOI, BEATRIZ E.. Cobalt(II) complexes of a alpha-diimine derived from cycloalkylamines as controlling agents for organometallic mediated radical polymerization of vinyl acetate. Polyhedron, v. 192, DEC 1 2020. (18/19395-9, 18/06340-1)

SILVA, TIAGO B.; MARTINS, DANIELE M.; GOIS, PATRIK D. S.; BORIM, PATRICIA; MAIA, PEDRO I. S.; CARVALHO, JR., VALDEMIRO P.; LIMA-NETO, BENEDITO S.. fac-[RuCl2(DMSO-S)(3)(n-butylamine)]: Synthesis, structural characterization and dual catalytic performance. Inorganic Chemistry Communications, v. 112, FEB 2020. (18/06340-1, 17/06329-5)

VANESSA B. VIEIRA; ELIADA A. DA SILVA; VALDEMIRO P. CARVALHO JR.; BENEDITO S. LIMA-NETO; JOSÉ L. S. SÁ. INFLUÊNCIA DO IMPEDIMENTO ESTÉRICO DE LIGANTES ANCILARES EM COMPLEXOS A BASE DE Ru APLICADOS EM METÁTESES DO ÁLCOOL E ACETATO CINAMÍLICOS. Química Nova, v. 43, n. 1, p. 24-31, 2020-03-16. (18/06340-1)

OLIVEIRA, DOUGLAS P.; CRUZ, THAIS R.; MARTINS, DANIELE M.; MAIA, PEDRO IVO S.; MACHADO, ANTONIO E. H.; BOGADO, ANDRE L.; GOI, BEATRIZ E.; LIMA-NETO, BENEDITO S.; CARVALHO-JR, VALDEMIRO P.. In situ-generated arene-ruthenium catalysts bearing cycloalkylamines for the ring-opening metathesis polymerization of norbornene. CATALYSIS TODAY, v. 381, p. 34-41, DEC 1 2021. (18/06340-1, 17/06329-5)

MARTINS, DANIELE M.; MAIA, PEDRO I. S.; CARVALHO-JR, VALDEMIRO P.; LIMA-NETO, BENEDITO S.. Cooperative Effects of Aniline with DMSO in Ru-II Complexes: Tuning the Reactivity for Ring-Opening Metathesis Polymerization. European Journal of Inorganic Chemistry, v. 2019, n. 41, p. 4421-4426, NOV 10 2019. (18/06340-1, 17/06329-5)

DE SANTANA GOIS, PATRIK DIONE; PEREIRA MAIA, JULIANA IRIS; CICERO MASSON, GUSTAVO HENRIQUE; MARTINS, DANIELE MARIA; DA HORA MACHADO, ANTONIO EDUARDO; GOI, BEATRIZ ELEUTERIO; DA SILVA MAIA, PEDRO IVO; DE CARVALHO-JR, VALDEMIRO PEREIRA. onometallic and heterobimetallic ruthenium (II) and palladium (II) complexes based on a pyridine-hydrazone ligand as bifunctional catalysts for ROMP of norbornene and ethylene polymerizatio. Applied Organometallic Chemistry, v. 36, n. 2, OCT 2021. (18/06340-1, 18/19395-9)

HASHIMOTO, PATRICIA K.; OLIVEIRA, LARISSA F.; RIGA-ROCHA, BEATRIZ A.; MACHADO, ANTONIO E. H.; SANTANA, VINICIUS T.; NASCIMENTO, OTACIRO R.; CARVALHO-JR, VALDEMIRO P.; GOI, BEATRIZ E.. Manganeseth(II) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate. NEW JOURNAL OF CHEMISTRY, v. 45, n. 22, p. 10109-10117, JUN 14 2021. (18/19395-9, 18/06340-1)

CRUZ, THAIS R.; SILVA, ELIADA A.; OLIVEIRA, DOUGLAS P.; MARTINS, DANIELE M.; GOIS, PATRIK D. S.; MACHADO, ANTONIO E. H.; MAIA, PEDRO IVO S.; GOI, BEATRIZ E.; LIMA-NETO, BENEDITO S.; CARVALHO-JR, VALDEMIRO P.. Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations. APPLIED ORGANOMETALLIC CHEMISTRY, v. 34, n. 5, p. 12-pg., 2020-02-20. (17/06329-5, 18/06340-1)