Catalytic CO2 transformation signified a paradigm shift towards the fabrication of contemporary chemical energy. The abundance of CO2 and the impending storage of fossil building blocks, has led to the proposal that CO2 should be the C1‐building block of the future. This doctoral thesis based on the development of an efficient homogeneous Ru‐catalytic system in ionic liquids, and its exploitation for Ru‐catalyzed carbonylations reactions with CO2 as CO source. Primarily synthesized task‐specific ionic Liquids for the generation of an active homogeneous Ru‐catalytic system by reacting with Ru3(CO)12 precursor. Then reaction was optimized for the Ru‐catalyzed selective hydroformylation of alkenes with CO2, and also investigated the mechanistic insight (Chapter‐ 3). The reaction of 1methyl3nbutylimidazolium chloride [BMI•Cl], or 1nbutyl2,3dimethyl limidazolium Chloride [BMMI•Cl] with Ru3(CO)12 generates Ru‐hydride‐carbonylcarbene species insitu that are efficient catalysts for Reverse Water Gas‐Shift (RWGS) / hydroformylation / hydrogenation cascade reaction. The addition of H3PO4 increases the catalytic activity of the first step (i.e., the reduction of CO2 to CO). Under optimized reaction conditions (120 ºC and 60 bar CO2/H2 (1:1) for 17 h), cyclohexene and 2,2‐disubstituted alkenes were easily functionalized to alcohols via a sequential hydroformylation‐carbonyl reduction by hydride transfer and protonolysis. These active Ru‐hydride‐carbonyl‐carbene species further strongly catalyzed the selective hydroaminomethylation of alkenes, and Nformylation amines with CO2 as CO source (Chapter‐4). Addition of P(OEt)3 and H3PO4 substantially and selectively formed hydroaminomethylation of alkenes, and N‐fomylation of amines, while N‐methylation of amines was not observed. The Insitu generated Ru‐hydride‐cabonyl‐carbene species are more efficient towards carbonylations of alkenes as compared to N‐formylation of amines. Furthermore mechanistic studies revealed hydroaminomethylation of alkenes involve in a sequence of RWGSR / hydroformylation / reductive amination by hydrogenation of imines and enamines intermediates. Interestingly, in the presence of stable phosphine additives the same catalytic system promoted N‐methylation of amines, and hydrogenation of alkenes. These findings of the CO2 transformation provided a new and highly valuable opportunity to get advantage of abundant CO2 as CO source for important industrial carbonylation processes, such as for the production of fragrances, and useful chemicals. Furthermore, the thesis work included the synthesis of well‐distributed Pd‐NPs (ca. 3.7 nm) deposited onto active carbon by magnetron‐sputtering process. Subsequently the catalytic performances were evaluated in the super hydrogenation of model of model substrates (i.e., nitrobenzene, 1,3‐cyclohexadiene and cyclohexene) at 75ºC under 4 bar dihydrogen (H2). The catalytic results revealed improved efficiencies in terms of activity and selectivity to those displayed by commercially available catalyst. Disproportion of 1,3‐cyclohexadiene and cyclohexene were revealed also as active processes under reaction conditions.
| Identifer | oai:union.ndltd.org:IBICT/oai:lume.ufrgs.br:10183/143860 |
| Date | January 2016 |
| Creators | Ali, Meher |
| Contributors | Dupont, Jairton |
| Source Sets | IBICT Brazilian ETDs |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis |
| Format | application/pdf |
| Source | reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, instname:Universidade Federal do Rio Grande do Sul, instacron:UFRGS |
| Rights | info:eu-repo/semantics/openAccess |
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