Synthesis of new organometallic complexes of Fe (III), Co (III) and Ni (III) coordinated to asymmetric Schiff bases to mediate photo-OMRP

• Grant number: 18/19395-9
• Support Opportunities: Regular Research Grants
• Start date: February 01, 2019
• End date: January 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Principal Investigator: Beatriz Eleutério Goi Carvalho
• Grantee: Beatriz Eleutério Goi Carvalho
• Host Institution: Faculdade de Ciências e Tecnologia (FCT). Universidade Estadual Paulista (UNESP). Campus de Presidente Prudente. Presidente Prudente , SP, Brazil

Abstract

Organometallic complexes of FeIII, CoIII and NiIII will be synthesized to mediate / control organometallic-mediated radical photopolymerization reactions - Photo-OMRP (Organometallic-Mediated Radical Polymerization). The proposal is to systematically evaluate different combinations of coordinate ancillary ligands to different transition metals and, consequently, to achieve a fine adjustment through the variation of the electronic and steric contributions in the metallic center, directing the reactivity of these organometallic complexes to act efficiently in the photo-OMRP. The ligands evaluated will be different unpublished asymmetric Schiff bases coordinated to the metal center of Fe, Co or Ni versus the polymerization of vinyl monomers via photo-OMRP. The proposal extends in three stages, which are completely interconnected in the development process. Initially, the attention will be focused on the synthesis of tetradentate asymmetric Schiff bases. The second step will be focused on the synthesis of the Fe (II), Ni (II) and Co (II) complexes coordinated with the different Schiff base ligands. The third step will be dedicated to the evaluation of the efficiency of Fe (II), Ni (II) and Co (II) complexes in the photo-OMRP reaction. The final step will be to select the Fe (II), Ni (II) and Co (II) complexes with the best performances and submit them to an addition reaction with the radical generated by the photochemical cleavage of a symmetric primer for obtain the organometallic complexes (III). It is intended, therefore, to establish fundamentals for the understanding of the performance of the mediators, as well as the formation of the reaction intermediates involved in each reaction, allowing the planning of systems that combine reactivity and selectivity for the synthesis of new materials with differentiated architecture via photo-OMRP. (AU)

Scientific publications

(7)

(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)

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)

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)

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)

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)

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)

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)