Utilization of CO2 as a solvent
Carbon dioxide can be a good alternative to organic solvents, often toxics and harmful for the environment.
We are currently interested in using the carbon dioxide, in supercritical or liquid phase, as a solvent in catalysed processes.
We are studying mainly the following reactions:
- Obtention of aldehydes by hydroformylation of alkenes.
The most efficient and less contaminant way to obtain aldehydes is by reaction of one olefin, carbon monoxide and hydrogen catalysed with a transition metal complex. In this area we have developed a series of catalyst adapted to be used in supercritical carbon dioxide. You can find more information in the following papers:
- New ligands for Rh-hydroformylation of 1-octene in supercritical carbon dioxide. X-ray structure of [Rh{PPh2(OC9H19)}4]PF6
M. Giménez-Pedrós, A. Aghmiz, N. Ruiz, A. M. Masdeu-Bultó
European Journal of Inorganic Chemistry, 2006, 1067-1075
- Hydroformylation of alkenes with rhodium catalyst in supercritical carbon dioxide
M. Giménez Pedrós, A. M. Masdeu-Bultó, J. Bayardon, D. Sinou
Catalysis Letters, 2006, 107, 205-208
Collaboration in this area with Prof. Denis Sinou (Université Claude Bernard, Lyon, França)
- New rhodium catalytic systems with trifluoromethyl phosphite derivatives for the hydroformylation of 1-octene in supercritical carbon dioxid
C. Tortosa Estorach, A. Orejón, A. M. Masdeu-Bultó.
Green Chemistry, 2008, 10, 545-552
- Hydroformylation of 1-Octene in Supercritical Carbon Dioxide with Rhodium Alkyl P-donor Ligands Using a Peracetylated ß-Cyclodextrin as Solubiliser
C. Tortosa Estorach, M. Giménez-Pedrós, A. M. Masdeu-Bultó, A. D. Sayede, E. Monflier.
European Journal of Inorganic Chemistry, 2008, 2659-2663
Collaboration in this area with Prof. Eric Monflier (Université de Lens, Lens, França)
- Obtention of acids through carbonilation of alkenes.
The reaction of an olefin with water or an alcohol leads to the carboxilic acids or the esters with the maximal atom economy.
You can find information about the catalytic systems that we have developped in the following publications:
- Hydrocarboxylation of terminal alkenes in supercritical carbon dioxide using perfluorinated surfactants
C. Tortosa Estorach, N. Ruiz, A. M. Masdeu-Bultó,
Chemical Communications, 2006, 2789-2791
- Hydroesterification of 1-alkenes in supercritical carbon dioxide
C. Tortosa, A. M. Masdeu-Bultó
Catalysis Letters, 2008, 122, 76-79
- Hydrocarboxylation of terminal alkenes in supercritical carbon dioxide
C. Tortosa Estorach, A. Orejón, N. Ruiz, A. M. Masdeu-Bultó, G. Laurenczy
European Journal of Inorganic Chemistry, 2008,22, 3524-3531
Collaboration in this area with Prof. Gabor Laurenczy (Université Polytecnique de Lausanne, Suissa)
- Obtention of poliketones from alkenes and carbon monoxide.
Poliketones are functionalised polymers with potential applications as thermoplastics. We have prepared a series of palladium catalysts for this reaction.
The detailed description is in the following publication:
- Alternating CO/tert-butylstyrene copolymerisation using soluble cationic palladium complexes in supercritical carbon dioxide
M. Giménez Pedrós, C. Tortosa-Estorach, A. Bastero, A. M. Masdeu-Bultó, M. Solinas, W. Leitner
Green Chemistry, 2006 , 8, 875-877.
Collaboration in this area with Prof. Walter Leitner ( Institut für Technische und Makromolekular Chemie, Aachen, Alemanya)
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Cationic palladium(II) complexes for CO/vinyl arene copolymerization in the presence of carbon dioxide.
A. Campos-Carrasco, C. Tortosa Estorach, A. Bastero, M. Reguero, A. M. Masdeu-Bultó, G. Franciò, W. Leitner, A. D’Amora, B. Milani
Organometallics, 2011, 30, 6572-6586
- Pd(II) complexes with 3,3'-substituted bipyridine ligands: synthesis, crystal structure and catalytic studies in compressed carbon dioxide
A. Campos-Carrasco, M. Bruce, M. Reguero and A. M. Masdeu-Bultó
Inorganica Chimica Acta, 2013, en revisió
The funding for this project comes from:
- Ministerio de Ciencia y Tecnología, PPQ2001-0452, CTQ2004-03831/PPQ, CTQ2007-63510/PPQ, ctq2010-16676
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