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Development of [RuCl2(PPh3)2(amine)] complex types for ring opening metathesis polymerization

Grant number: 11/12571-7
Support type:Scholarships in Brazil - Doctorate (Direct)
Effective date (Start): January 01, 2012
Effective date (End): September 30, 2016
Field of knowledge:Physical Sciences and Mathematics - Chemistry
Principal Investigator:Benedito dos Santos Lima Neto
Grantee:Larissa Ribeiro da Fonseca
Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
Associated scholarship(s):12/23948-7 - Correlation between the properties of the polymers and biopolymers obtained by ROMP with [RuCl2(PPh3)2(amine)] complex types, BE.EP.DD


This research aims to study the catalytic activity of complexes when modifying the sigma-donor ability in coordinated amines. Different electronic and steric hindrance combinations in the ancillary ligands can tune the Ru metal center reactivity, with implications in the polymer characteristics. Thus, [RuCl2(PPh3)2(amina)] complex types will be obtained for Ring Opening Metathesis Polymerization (ROMP) of the cyclic olefins norbornene (NBE), norbonadiene (NBD) and dicyclopentadiene (DCPD). The reaction will be carried out in presence of ethyldiazoacetate (EDA) and investigated as a function of the temperature, reaction time, solvent volume, absence/presence of O2 (atmosphere of argon or air), monomer and complex concentrations for a certain solvent volume. The complex reactivities will be observed considering the reaction yields from the isolated polymers, molecular weights, stereochemistry and thermal features. Initiation and propagation rate measurements of will be performed. Syntheses de poli[NBE-co-NBD] and poli[NBE-co-DCPD] will be carried out, observing the intercrossing degrees and the reactivity ratios. The investigated amines as ancillary ligands will be pyrrolidine (HN(CH2)4), azocane (HN(CH2)7) e diethilamine (HN(CH2CH3)2). In addition, deprotonation of the amines will take place using KN(SiMe3)2, to produce K[RuCl2(PPh3)2(amina aniônica)] complex types. The complexes will be characterized for elemental analyses, infrared, UV-Vis spectrophotometry, NMR (31P; 1H) andcyclic voltametry. The polymers will be characterized for GPC, NMR (1H; 13C), TGA and DMA. (AU)

Scientific publications (4)
(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)
FONSECA, LARISSA R.; SILVA SA, JOSE L.; CARVALHO, JR., VALDEMIRO P.; LIMA-NETO, BENEDITO S. Cross-link in norbornadiene-based polymers from ring-opening metathesis polymerization with pyrrolidine-based Ru complex. POLYMER BULLETIN, v. 75, n. 8, p. 3705-3721, AUG 2018. Web of Science Citations: 2.
SILVA, RODOLPHO A. N.; BORIM, PATRICIA; FONSECA, LARISSA R.; LIMA-NETO, BENEDITO S.; SILVA SA, JOSE L.; CARVALHO-, JR., VALDEMIRO P. Non-carbene Complex [RuCl2(PPh3)(2)(azocane)] as Active Catalyst Precursor for ROMP and ATRP. CATALYSIS LETTERS, v. 147, n. 5, p. 1144-1152, MAY 2017. Web of Science Citations: 5.
FERRAZ, C. P.; FONSECA, L. R.; TOMAZETTI, V.; SILVA, F. C. S.; LIMA-NETO, B. S.; CARVALHO, JR., V. P. Copolymers from norbornene and norbornadiene with organized morphologies and high T-g values obtained via ROMP with a highly reactive [RuCl3(PCy3)(2)] complex. NEW JOURNAL OF CHEMISTRY, v. 40, n. 11, p. 9424-9431, 2016. Web of Science Citations: 4.
FONSECA, LARISSA R.; NASCIMENTO, EDUARDO S. P.; SILVA SA, JOSE L.; LIMA-NETO, BENEDITO S. The ring size of cyclic amines as a relevant feature in the activity of Ru- based complexes for ROMP. NEW JOURNAL OF CHEMISTRY, v. 39, n. 5, p. 4063-4069, 2015. Web of Science Citations: 9.
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
FONSECA, Larissa Ribeiro da. Syntheses of ruthenium-amine-based complexes and its applications in metathesis reactions: ring opening metathesis polymerization, cross metatathesis and selfmetathesis. 2016. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos São Carlos.

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