dc.creator | Martínez Prieto, Luis Miguel | es |
dc.creator | Palma Ramírez, María del Pilar | es |
dc.creator | Cámpora Pérez, Juan | es |
dc.date.accessioned | 2022-10-07T10:49:47Z | |
dc.date.available | 2022-10-07T10:49:47Z | |
dc.date.issued | 2019 | |
dc.identifier.citation | Martínez Prieto, L.M., Palma Ramírez, M.d.P. y Cámpora Pérez, J. (2019). Monomeric alkoxide and alkylcarbonate complexes of nickel and palladium stabilized with the iPrPCP pincer ligand: a model for the catalytic carboxylation of alcohols to alkyl carbonates. Dalton Transactions [English] ISSNs Print: URL http://pubs.rsc.org/en/Journals/JournalIssues/DT Publishers, 48 (4), 1351-1366. https://doi.org/10.1039/c8dt04919j. | |
dc.identifier.issn | 1477-9226 | es |
dc.identifier.issn | 1477-9234 | es |
dc.identifier.uri | https://hdl.handle.net/11441/137716 | |
dc.description.abstract | Monomeric alkoxo complexes of the type [(iPrPCP)M-OR] (M = Ni or Pd; R = Me, Et, CH2CH2OH; iPrPCP =
2,6-bis(diisopropylphosphino)phenyl) react rapidly with CO2 to afford the corresponding alkylcarbonates
[(iPrPCP)M-OCOOR]. We have investigated the reactions of these compounds as models for key steps of
catalytic synthesis of organic carbonates from alcohols and CO2. The MOCO-OR linkage is kinetically
labile, and readily exchanges the OR group with water or other alcohols (R’OH), to afford equilibrium mixtures containing ROH and [(iPrPCP)M-OCOOH] (bicarbonate) or [(iPrPCP)M-OCOOR’], respectively.
However, [(iPrPCP)M-OCOOR] complexes are thermally stable and remain indefinitely stable in solution
when these are kept in sealed vessels. The constants for the exchange equilibria have been interpreted,
showing that CO2 insertion into M-O bonds is thermodynamically more favorable for M-OR than for
M-OH. Alkylcarbonate complexes [(iPrPCP)M-OCOOR] fail to undergo nucleophilic attack by ROH to yield
organic carbonates ROCOOR, either intermolecularly (using neat ROH solvent) or in intramolecular
fashion (e.g., [(iPrPCP)M-OCOOCH2CH2OH]). In contrast, [(iPrPCP)M-OCOOMe] complexes react with a
variety of electrophilic methylating reagents (MeX) to afford dimethylcarbonate and [(iPrPCP)M-X]. The
reaction rates increase in the order X = OTs < IMe ≪ OTf and Ni < Pd. These findings suggest that a suitable catalyst design should combine basic and electrophilic alcohol activation sites in order to perform
alkyl carbonate syntheses via direct alcohol carboxylation. | es |
dc.description.sponsorship | Ministerio de Economía y Competitividad de España (MINECO) y los fondos FEDER de la Unión Europea-CTQ2015-68978-P | es |
dc.format | application/pdf | es |
dc.format.extent | 16 p. | es |
dc.language.iso | eng | es |
dc.publisher | Royal Society of Chemistry | es |
dc.relation.ispartof | Dalton Transactions [English] ISSNs Print: URL http://pubs.rsc.org/en/Journals/JournalIssues/DT Publishers, 48 (4), 1351-1366. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Monomeric alkoxide and alkylcarbonate complexes of nickel and palladium stabilized with the iPrPCP pincer ligand: a model for the catalytic carboxylation of alcohols to alkyl carbonates | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/acceptedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Inorgánica | es |
dc.relation.projectID | CTQ2015-68978-P | es |
dc.relation.publisherversion | https://dx.doi.org/10.1039/c8dt04919j | es |
dc.identifier.doi | 10.1039/c8dt04919j | es |
dc.journaltitle | Dalton Transactions [English] ISSNs Print: URL http://pubs.rsc.org/en/Journals/JournalIssues/DT Publishers | es |
dc.publication.volumen | 48 | es |
dc.publication.issue | 4 | es |
dc.publication.initialPage | 1351 | es |
dc.publication.endPage | 1366 | es |
dc.contributor.funder | Ministerio de Economía y Competitividad (MINECO). España | es |
dc.contributor.funder | European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER) | es |