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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations

Texto completo
Autor(es):
Cruz, Thais R. [1] ; Silva, Eliada A. [2] ; Oliveira, Douglas P. [1] ; Martins, Daniele M. [2] ; Gois, Patrik D. S. [1] ; Machado, Antonio E. H. [3] ; Maia, Pedro Ivo S. [4] ; Goi, Beatriz E. [1] ; Lima-Neto, Benedito S. [2] ; Carvalho-Jr, Valdemiro P.
Número total de Autores: 10
Afiliação do(s) autor(es):
[1] UNESP Univ Estadual Paulista, Fac Ciencias Tecnol, BR-19060900 Presidente Prudente, SP - Brazil
[2] Univ Sao Paulo, Inst Quim Sao Carlos, BR-13560970 Sao Carlos, SP - Brazil
[3] Univ Fed Triangulo Mineiro, Inst Quim, POB 593, BR-38400089 Uberlandia, MG - Brazil
[4] Univ Fed Triangulo Mineiro, Dep Quim, BR-38025440 Uberaba, MG - Brazil
Número total de Afiliações: 4
Tipo de documento: Artigo Científico
Fonte: Applied Organometallic Chemistry; v. 34, n. 5 FEB 2020.
Citações Web of Science: 0
Resumo

Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(eta(6)-p-cymene)(pyrrolidine)] (1), {[}RuCl2(eta(6)-p-cymene)(piperidine)] (2), and {[}RuCl2(eta(6)-p-cymene)(peridroazepine)] (3) were successfully synthesized. Complexes 1-3 were fully characterized by means of Fourier transform infrared, UV-visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X-ray crystallography. These compounds were evaluated as catalytic precursors for ring-opening metathesis polymerization (ROMP) of norbornene (NBE) and atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1-3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different {[}NBE]/{[}EDA]/{[}Ru] ratios, temperatures (25 and 50 degrees C), and reaction times (5-60 min). The highest yields of polyNBE were obtained with {[}NBE]/{[}EDA]/{[}Ru] = 5000/28/1 for 60 min at 50 degrees C. MMA polymerization via ATRP was conducted using 1-3 as catalysts in the presence of ethyl-alpha-bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of {[}MMA]/{[}EBiB]/{[}Ru] = 1000/2/1 at 95 degrees C. The increase in molecular weight as function of time indicates that complexes 1-3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP. (AU)

Processo FAPESP: 17/06329-5 - Desenvolvimento de complexos de rutênio com aminas como ligantes ancilares para catálise homogênea de reações de polimerização de olefinas cíclicas via metátese
Beneficiário:Benedito dos Santos Lima Neto
Linha de fomento: Auxílio à Pesquisa - Regular
Processo FAPESP: 18/06340-1 - Complexos bimetálicos de rutênio(II) e níquel(II): acoplamento de reações mecanisticamente incompatíveis usando catalisadores multifuncionais via catálise tandem
Beneficiário:Valdemiro Pereira de Carvalho Júnior
Linha de fomento: Auxílio à Pesquisa - Regular