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Master's Dissertation
DOI
https://doi.org/10.11606/D.75.2008.tde-20062008-165939
Document
Author
Full name
Valdemiro Pereira de Carvalho Júnior
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2008
Supervisor
Committee
Lima Neto, Benedito dos Santos (President)
Mandelli, Dalmo
Moreira, Wania da Conceição
 
Title in Portuguese
Reatividade de complexos do tipo [RuCl2(S-dmso)2(NIII)2 para ROMP de norborneno
Keywords in Portuguese
DMSO
norborneno
ROMP
Abstract in Portuguese
Este trabalho reporta sínteses e caracterizações de complexos do tipo [RuCl2(S-dmso)2(N)III)2], onde NIII = piridina, isonicotinamida e nicotinamida. Os complexos foram aplicados em ROMP de norborneno de modo investigar os efeitos cooperativos entre os ligantes ancilares dmso e aminasneste tipo de reação. O complexo com nicotinamida apresentou a maior atividade catalítica em 60 min a 50 ºC (20% de rendimento; Mw / Mn = 1,98). Os outros complexos derivados foram praticamente inertes para ROMP. Usando uma solução envelhecida por 140 min a 50 ºC do complexo com isonicotinamida, não foi observada mudanças significativas na atividade catalítica por 60 min a 50 ºC (17% de rendimento; Mw / Mn = 4,24). Experimentos com uma solução do complexo com isonicotinamida na presença do sal NBu4ClO4, o rendimento foi de 19% (Mw / Mn = 1,78) mediante as mesmas condições. Usando soluções irradiadas com luz branca (5-10 min) à temperatura ambiente, os complexos com piridina e isonicotinamida mostraram rendimentos de 36% (Mw / Mn = 1,8) e 26% (Mw / Mn = 1,7) por 60 min a 50 ºC, respectivamente. O complexo [RuCl3 (Ph2SO) 3] foi também isolado e sua atividade em ROMP para norborneno foi de 33% (Mw / Mn = 1,32) à temperatura ambiente por 5 min. O rendimento aumentou para 58% (Mw / Mn = 1,41) a 50 ºC por 30 min. Na presença do sal NBu4ClO4, o rendimento de reação não apresentou mudanças significativas. Dos resultados obtidos, conclui-se que os ligantes dmso e as aminas estudadas podem ser empregados como ligantes ancilares em complexos de Ru(II) para as reações de ROMP, considerando um efeito cooperativo de sintonia eletrônica.
 
Title in English
Reactive of complexes [RuCl2(S-dmso)2(NIII)2 for ROMP of norbornene
Keywords in English
DMSO
norbornene
ROMP
Abstract in English
This work reports the synthesis and characterizations of [RuCl2(S-dmso)2(N)III)2] complexes, where NIII = pyridine, isonicotinamide and nicotinamide. The complexes were applied in ROMP of norbornene in order to investigate the cooperative effects among the dmso and amines as ancillary ligands in this kind of reaction. The complex with nicotinamide showed the highest catalytic activity for 60 min at 50 ºC (20% yield; Mw / Mn = 1,98). The other derivatives were roughing inert for ROMP. Using an aged solution for 140 min at 50 ºC of the isonicotinamide complex, it was observed a significant change in their catalytic activity for 60 min at 50 ºC (17% yield; Mw / Mn = 4,24). Experiments using isonicotinamide complex solution in presence of the salt NBu4ClO4, the yield was 19% (Mw / Mn = 1,78) under similar conditions. When using irradiated solution with white lamp (5-10 min) at room temperature, the pyridine (for 10 min) and isonicotinamide (for 5 min) complexes showed yields of 36% (Mw / Mn = 1,8) and 26% (Mw / Mn = 1,7) for 60 min at 50 ºC respectively. The complex [RuCl3 (Ph2SO) 3] was also isolated and the ROMP active for norbornene was 33% (Mw / Mn = 1,32) at room temperature for 5 min. The yield increased to 58% (Mw / Mn = 1,41) at 50 ºC for 30 min. In the presence of the salt NBu4ClO4, the yield showed no significant changes. It is concluded that the ligands dmso and the studied amines can be selectively used as ancillary ligands in Ru(II) complexes for ROMP reactions inside of an electronic tuning cooperative effect.
 
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ValdemiroJuniorR.pdf (5.51 Mbytes)
Publishing Date
2008-09-02
 
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