Synthesis of new heterobimetallic complexes of RuII/NiII and RuII/PdII as multifunctional catalysts in the coupling of mechanistically distinct polymerization reactions

• Grant number: 22/12417-2
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: March 01, 2023
• Status: Discontinued
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Valdemiro Pereira de Carvalho Júnior
• Grantee: Douglas Henrique Nunes Santos
• Host Institution: Faculdade de Ciências e Tecnologia (FCT). Universidade Estadual Paulista (UNESP). Campus de Presidente Prudente. Presidente Prudente , SP, Brazil
• Associated scholarship(s): 24/15926-0 - Synthesis of Ru-Pd Heterobimetallic Complexes as Bifunctional Catalysts for Tandem Suzuki-Miyaura/Transfer Hydrogenation, BE.EP.DR

Abstract

The coupling of mechanistically distinct reactions, ethylene polymerization, cyclic olefin polymerization via metathesis - ROMP and radical atom transfer polymerization - ATRP, 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 the heterobimetallic complexes of RuII/PdII and RuII/NiII and, consequently, to achieve a fine adjustment through the variation of the electronic and steric contributions in the metallic centers. In this way, 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/ROMP polymerization, and then, in the triple coupling: ethylene/ROMP/ polymerization ATRP. Initially, the research will focus on the catalytic activity of the complexes in the polymerization of ethylene, ROMP and ATRP separately, considering that a thorough understanding of the individual reactions is a key step in the development of multifunctional catalysts for the tandem catalysis of these reactions. It is intended, therefore, to establish foundations for understanding the performance of catalysts, as well as the formation of reaction intermediates involved in each reaction and, thus, enable the planning of multifunctional catalytic systems that combine reactivity and selectivity for the synthesis of new materials with differentiated architecture via tandem polymerization, aiming at technology transfer.