Development of ruthenium complexes with ammines as ancillary ligands for homogeneous catalysis of ring opening metathesis polymerization of cyclic olefins

• Grant number: 17/06329-5
• Support Opportunities: Regular Research Grants
• Duration: August 01, 2017 - January 31, 2020
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Benedito dos Santos Lima Neto
• Grantee: Benedito dos Santos Lima Neto
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil

Abstract

Ruthenium complexes with cyclic and acyclic amines will be developed to act as catalysts in reactions of ring-opening metathesis polymerization (ROMP). In addition to the ammines in the metal coordination sphere, phosphines, phosphites or sulfoxides will also be present as ancillary ligands. The strategy is to make electronic and steric hindrance combinations by using different ancillary ligands in the coordination sphere of the complex. In this way, the reactivity of the metal center can be controlled regarding the induction period for the formation of the active metal-carbene species, and especially with respect to the initiation and propagation rates in the polymerizations. The resulting complexes may present different affinities for the monomers, affecting the physico-chemical characteristics of the polymers, such as molar mass, polydispersity, degree of crosslinking, solubility, microstructure, thermal and mechanical properties, etc. A variety of unsaturated bicyclic monomers will be tested, e.g., norbornene and derivatives, 7-oxanorbornene and derivatives, norbornadiene, and dicyclopentadiene to obtain homopolymers and copolymers. The derivative parts inserted into the monomers are amides functionalized with fatty acids or N-heterocyclics and esters of fatty acids, all developed throughout the research. The research focuses on aspects of ROMP by considering individual reactions that are key steps in the catalytic cycle or that initiate it. It is intended to provide fundamentals for understanding the performance of pre-catalysts (initiators), and subsequently design chemical systems that combine catalytic activity and polymer syntheses with desirable characteristics, aiming at technology transfer. There is concern with the development of robust complexes that are resistant to storage and reactive in ambient atmosphere. (AU)

Scientific publications

(8)

(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)

FERNANDES, HENRIQUE; FILGUEIRAS, JEFFERSON G.; DE AZEVEDO, EDUARDO R.; LIMA-NETO, BENEDITO S.. Real time monitoring by time-domain NMR of ring opening metathesis copolymerization of norbornene-based red palm olein monomer with norbornene. EUROPEAN POLYMER JOURNAL, v. 140, NOV 5 2020. (17/24465-3, 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)

FERREIRA, MARCELLA S.; FERNANDES, HENRIQUE; SILVA SA, JOSE L.; CARVALHO, JR., VALDEMIRO P.; LIMA-NETO, BENEDITO S.. ROMP-based biorenewable polymers of norbornene modified with triglycerides or esters from natural buriti oil. POLYMER BULLETIN, v. 76, n. 10, p. 5399-5413, OCT 2019. (17/06329-5)

SOUSA, DENISE A.; MENESES, PAULO S.; GOIS, PATRIK D. S.; SILVA, ELIADA A.; JUNIOR, VALDEMIRO P. C.; LIMA-NETO, BENEDITO S.; SILVA SA, JOSE L.. Application of Amine-based Ru Compounds in the Olefin Metathesis of Methyl Eugenol: A Comparison with Grubbs Catalysts. Letters in Organic Chemistry, v. 17, n. 8, p. 596-602, 2020. (17/06329-5)

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)

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)

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)

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)