The ring size of cyclic amines as a relevant feature in the activity of Ru-based complexes for ROMP

Fonseca, Larissa R.; Nascimento, Érika; Sá, José Luiz Silva; Neto, Benedito dos Santos Lima

doi:10.1039/c5nj00321k

Cited by 19 publications

(26 citation statements)

References 27 publications

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“…An alternative to these catalysts is the development of highly active and robust compounds that can be easily prepared at low production cost. In our Inorganic and Analytic Chemistry Group in Brazil, non‐carbene Ru‐based complexes have been synthesized and applied successfully in Ring Opening Metathesis Polymerization (ROMP) reactions . There has been considerable effort in our research group to tune the ancillary ligands in [RuCl 2 (amine) x (PR 3 ) y ] complexes, in search of alternative catalysts for ROMP.The main characteristic of these complexes is the in‐situ formation of the catalytic species (metal‐carbene) from ethyl diazoacetate (EDA).…”

Section: Introductionmentioning

confidence: 99%

Self‐Metathesis of 10‐Undecen‐1‐Ol with Ru‐Amine‐Based Complex for Preparing the Soft Segment and Chain Extender of Novel Castor Oil‐Based Polyurethanes

Fonseca

Bergman

Kessler

et al. 2016

Macromolecular Symposia

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Summary Self‐metathesis of the terminal olefin in 10‐undecen‐1‐ol was conducted in the presence of [RuCl2(PPh3)2(perhydroazepine)] complex and ethyl diazoacetate (EDA) to form a bioderived diol. The diol was utilized as soft segment and chain extender in polyurethane reactions with castor oil. Polymers with high Mw and Mn values and PDI's of 2 and 3 were obtained. The viscoelastic material parameters (G′, G″ and η*) were studied as a function of angular frequency at different temperatures and diol/castor oil compostions. Newtonian behavior was observed for these materials. Tg values were more negative when increasing the diol percentage because the material became more viscoelastic. At only 10 wt% of the diol, an adhesive characteristic was observed in the castor oil‐based polyurethane. Modifying the castol oil‐based polyurethane with 10 wt% of the diol was able to modify the rigid polyurethane, providing an adhesive characteristic to castor oil‐based polyurethane.

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Section: Introductionmentioning

confidence: 99%

Self‐Metathesis of 10‐Undecen‐1‐Ol with Ru‐Amine‐Based Complex for Preparing the Soft Segment and Chain Extender of Novel Castor Oil‐Based Polyurethanes

Fonseca

Bergman

Kessler

et al. 2016

Macromolecular Symposia

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“…The yields or selectivity are achieved by tuning the choice of the catalyst with the reaction conditions [12]. In this way, the application of catalytic precursors, such as the Lima-Neto Ru-compounds synthesized for ROMP reactions [13][14][15][16], can be modulated for other purposes inside of the metathesis type.…”

Section: Of 11mentioning

confidence: 99%

Ethyl Linoleate Derivatives from Olefin Metathesis as a Function of the Starting Complex and Reactivity Conditions

Neta¹,

Silva²,

Carvalho³

et al. 2017

Preprint

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Olefin metathesis of ethyl linoleate (EL) was investigated under different conditions of substrate amount, temperature, and catalyst. Second-generation Grubbs catalyst (G2) was used in experiments at 20 and 50 ºC for 24 and 48h, whereas first-generation Grubbs catalyst (G1) and [RuCl2(PPh3)2perhydroazepine] (LN) were used in experiments at 50 ºC for 24h, with the latter also being investigated in the presence or absence of SnCl2 as co-catalyst. Catalytic products were analyzed for GC-MS and discussed in terms of relative percent of the metathesis products. With G2 as catalyst, GC-MS chromatograms were similar in all the amounts of EL investigated at 50 ºC for 24h, except for ethyl hexadec-9-enoate (compound K), which was obtained with different percentage as a function of EL amount (55% for 2 and 5 mL and 65% for 8 mL). An α,ω-dicarboxylic acid with m/z = 444.00 (compound L) was produced from the experiments at 50 ºC for 24h with similar percentage as a function of EL amount. However, the relative percentage of L changed with the increase of EL volume in the experiments at 20 ºC (ca. 18, 27, and 28%, with 2, 5, and 8 mL of EL, respectively). The olefin metathesis of EL conducted by G1 reached lower selectivity than that conducted by G2 for 24h at 50 ºC. Several intense peaks reached with G1 were similar to those obtained with G2, in addition to new peaks of medium intensity. Compound L showed higher m/z, similar to that presented with G2, but with lower relative proportion in the mixture. LN was inert for olefin metathesis of EL; however, it was activated in the presence of SnCl2 at 50 ºC for 24h. Different compounds and selectivity as a function of the catalyst type and reaction conditions were obtained.

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“…O aumento da temperatura pode favorecer a labilização da fosfina da esfera de coordenação do metal, e com isso o olefina pode coordena-se ao metal cisposicionada ao carbeno, facilitando a ROMP. Esse comportamento também foi observado em outros sistemas catalíticos já investigados pelo Grupo 13,35,42 . Fonte: Autoria própria.…”

Section: -Resultados E Discussãounclassified

“…Esse fenômeno também explica de certa forma, uma leve diminuição nos valores de rendimentos dos poliNBE obtidos em atmosfera aberta. 42,46 .…”

Section: -Polimerização Em Atmosfera De Arunclassified

Desenvolvimento de complexo de Ru(II) com 3-metilpiperidina para atuar como catalisador em reações de polimerização via metátese de olefinas cíclicas

Pereira¹

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The ring size of cyclic amines as a relevant feature in the activity of Ru-based complexes for ROMP

Abstract: The ring size of cyclic amines influences the yield, Mw and PDI values of polynorbonene obtained via ROMP using [RuCl2(PPh3)2(amine)x] as the starting complex.

Cited by 19 publications

References 27 publications

Self‐Metathesis of 10‐Undecen‐1‐Ol with Ru‐Amine‐Based Complex for Preparing the Soft Segment and Chain Extender of Novel Castor Oil‐Based Polyurethanes

Self‐Metathesis of 10‐Undecen‐1‐Ol with Ru‐Amine‐Based Complex for Preparing the Soft Segment and Chain Extender of Novel Castor Oil‐Based Polyurethanes

Ethyl Linoleate Derivatives from Olefin Metathesis as a Function of the Starting Complex and Reactivity Conditions

Desenvolvimento de complexo de Ru(II) com 3-metilpiperidina para atuar como catalisador em reações de polimerização via metátese de olefinas cíclicas

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