[en] Heterobimetallic complexes offer greater versatility for applications in homogeneous catalysis than their monometallic counterparts. To take advantage of this synergy, three [Pd(N,N,S-TSC)(4-NH2Py)] complexes (mono-PdMe, mono-PdMe,Me and mono-PdPh) were synthesized from [PdCl2(MeCN)2] and appropriate thiosemicarbazide (TSC) ligand precursors, followed by the addition of 4-aminopyridine (4-NH2Py). The reaction of these mono-PdL complexes with [RuCl2(η6-p-cymene)]2 then afforded three heterobimetallic complexes with the generic formula [{RuCl2(p-cymene)}-μ-{(4-NH2Py)Pd (TSC)}] (Ru-PdMe, Ru-PdMe,Me and Ru-PdPh). All these novel compounds were characterized by elemental analysis, spectroscopic techniques, cyclic voltammetry, and density functional theory (DFT) calculations. The molecular structure of mono-PdMe was determined by X-ray diffraction analysis. The Ru-PdL complexes were evaluated as bifunctional catalysts in the reductive Heck coupling of norbornadiene (NBD) with iodobenzene and the ring-opening metathesis polymerization (ROMP) of phenylnorbornene (Ph-NBE). They were very active for the reductive Heck reaction, reaching yields higher than 90% when a [Pd]/[NBD]/[PhI] ratio of 1/418/1344 was employed at 120°C. Upon activation with ethyl diazoacetate (EDA), they were also able to polymerize Ph-NBE with yields around 70% using a [Ph-NBE]/[Ru-PdL] ratio of 3000 at 50°C for 30 min. The Ru-PdMe,Me complex showed the highest activity in the ROMP of Ph-NBE and was successfully applied for mediating the synthesis of poly (Ph-NBE) from NBD via tandem catalysis.
Disciplines :
Chemistry
Author, co-author :
Cruz, Thais R.; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, Brazil ; Laboratory of Catalysis, Institut de Chimie Organique (B6a), Allée du six Août 13, Université de Liège, Liège, Belgium
Maia, Juliana I. P. ; Instituto de Ciências Exatas, Naturais e Educação, Universidade Federal do Triângulo Mineiro, Uberaba, Brazil
Maia, Pedro I. S.; Instituto de Ciências Exatas, Naturais e Educação, Universidade Federal do Triângulo Mineiro, Uberaba, Brazil
Machado, Antonio E. H.; Instituto de Química, Universidade Federal de Uberlândia, Uberlândia, Brazil ; Programa de Pós-Graduação em Ciência e Engenharia de Materiais, Universidade Federal de Catalão, Catalão, Brazil
Goi, Beatriz E.; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, Brazil
Delaude, Lionel ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Carvalho-Jr, Valdemiro P. ; São Paulo State University (Unesp), School of Technology and Sciences, Presidente Prudente, Brazil
Language :
English
Title :
Heterobimetallic Pd-Ru Catalysts for the Synthesis of Functionalized Polynorbornenes via Reductive Heck/ROMP Reactions
FAPESP - Fundação de Amparo à Pesquisa do Estado de São Paulo CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
Funding text :
This research was funded by the CNPq (grant 311747/2023\u20100), FAPEMIG (RED\u201000116\u201023) and FAPESP (grant 2021/13128\u20101 and Proc. 2021/11873\u20101). The authors acknowledge the financial support provided by PROPe/UNESP through the public call Edital 04/2024. The financial support of CNPq (Proc. 88881.690136/2022\u201001) is gratefully acknowledged (sandwich doctoral fellowship to TRC). The Article Processing Charge for the publication of this research was funded by the Coordena\u00E7\u00E3o de Aperfei\u00E7oamento de Pessoal de N\u00EDvel Superior \u2010 Brasil (CAPES) (ROR identifier: 00x0ma614).Funding: This work was supported by the Funda\u00E7\u00E3o de Amparo \u00E0 Pesquisa do Estado de S\u00E3o Paulo (2021/13128-1, 2021/11873-1), Conselho Nacional de Desenvolvimento Cient\u00EDfico e Tecnol\u00F3gico (311747/2023-0, 88881.690136/2022-01), and Funda\u00E7\u00E3o de Amparo \u00E0 Pesquisa do Estado de Minas Gerais (RED-00116-23). This research was funded by the CNPq (grant 311747/2023-0), FAPEMIG (RED-00116-23) and FAPESP (grant 2021/13128-1 and Proc. 2021/11873-1). The authors acknowledge the financial support provided by PROPe/UNESP through the public call Edital 04/2024. The financial support of CNPq (Proc. 88881.690136/2022-01) is gratefully acknowledged (sandwich doctoral fellowship to TRC). The Article Processing Charge for the publication of this research was funded by the Coordena\u00E7\u00E3o de Aperfei\u00E7oamento de Pessoal de N\u00EDvel Superior - Brasil (CAPES) (ROR identifier: 00x0ma614).
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