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Ruthenium-palladium heterobimetallic complex as a multifunctional catalyst for ROMP and ethylene polymerization
Patrik Dione de Santana Gois
Universidade Estadual Paulista “Júlio de Mesquita Filho”
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Create a topicInvestigations on new reactions using the well-defined catalysts for olefin metathesis and ethylene polymerization have been occurred around the world.1,2 On the other hand, there is a stimulating challenge in the search for simpler systems, in which an active catalytic species could be readily generated in-situ at low cost. In this direction, we have been developing of alternative Ru/Pd-based catalyst, the novel ruthenium-palladium heterobimetallic complex was synthesized in two steps, [Pd(PPh3)(DMSIO)] (1) synthesis, which reacted with [RuCl2(p-cymene)]2 giving the bimetallic [RuCl2(p-cymene)-Pd(PPh3)(DMSIO)] (2). The complex [RuCl2(p-cymene)(isoniazid)] (3) was synthetized according to the literature2 to compare its reactivity with complex 2. The complexes were characterized by FTIR, UV-Vis and 1H, 13C{1H} and 31P{1H} NMR.
The complexes 2 and 3 were evaluated as catalytic precursors for ROMP of norbornene (NBE) and the complex 3 has been evaluated for ethylene polymerization. The polynorbornene (polyNBE) syntheses via ROMP using the complexes 2 and 3 as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 mL), [NBE]/[Ru] = 3500 for 60 minutes at 50 °C, both the complexes were active and the yields were 12 and 17 % respectively. The polymerization of ethylene mediated by palladium complex precursor 1 was active using MAO (Methylaluminoxane) as initiator with a [MAO]/[Pd] ratio of 700, then the complex 2 will be evaluated in the same conditions.
Murillo da Silva Paiano
Parabéns pelo trabalho desenvolvido!
Vejo que o complexo bimetálico foi caracterizado por DRX, sendo assim você conseguiu cristais do composto?
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Patrik Dione de Santana Gois
Obrigado pelo elogio.
Como foi falado na apresentação, conseguimos apenas o cristal da espécie monometálica de paládio para a realização de DRX, estamos tentando algumas técnicas de cristalização para conseguir o cristal da espécie bimetálica também.
Obrigado pela pergunta.