dc.creator | Martínez Prieto, Luis Miguel | es |
dc.creator | Álvarez González, Eleuterio | es |
dc.creator | Palma Ramírez, María del Pilar | es |
dc.creator | Cámpora Pérez, Juan | es |
dc.creator | Río, Diego del | es |
dc.date.accessioned | 2022-10-14T17:12:09Z | |
dc.date.available | 2022-10-14T17:12:09Z | |
dc.date.issued | 2021 | |
dc.identifier.citation | Martínez Prieto, L.M., Álvarez González, E., Palma Ramírez, M.d.P., Cámpora Pérez, J. y Río, D.d. (2021). Nucleophilic Nickel and Palladium Pincer Hydroxides: A Study of Their Reactions with Dimethyl Carbonate and Other Non-Alkylating Organic Electrophiles. European Journal of Inorganic Chemistry, 2021 (29), 2958-2975. https://doi.org/10.1002/ejic.202100400. | |
dc.identifier.issn | 1434-1948 | es |
dc.identifier.issn | 1099-0682 | es |
dc.identifier.uri | https://hdl.handle.net/11441/137934 | |
dc.description.abstract | The reactions of the pincer hydroxide complexes [(iPrPCP)M(OH)] (M=Ni, Pd) with dimethyl carbonate (DMC), and a set of organic electrophiles including benzaldehyde have been investigated in the context of our ongoing investigation on the synthesis of alkyl carbonates from CO2 and alcohols. The final outcome of such reactions is diverse, but for PhCHO and DMC the first step is a mechanistically similar addition of the [M]−OH linkage across the carbonyl functionality, that leads to unstable adducts. DMC is cleaved irreversibly by both Ni and Pd hydroxides, affording the corresponding methylcarbonates [(iPrPCP)MOCO2Me] and methanol, whereas PhCHO affords benzoate complexes [[(iPrPCP)MOCO2Ph]. The main kinetic and thermodynamic features of these reactions were reproduced satisfactorily by computational DFT models. The calculations throw light on the true causes of irreversibility of DMC cleavage by nucleophilic hydroxide complexes, which is the primary cause that prevents methanol carboxylation from being catalysed by the Ni or Pd pincers. | es |
dc.description.sponsorship | Agencia Estatal de Investigación PGC2018-095768-B-100 | es |
dc.description.sponsorship | Junta de Andalucía PY20_0104 | es |
dc.format | application/pdf | es |
dc.format.extent | 19 p. | es |
dc.language.iso | eng | es |
dc.publisher | Wiley-Blackwell | es |
dc.relation.ispartof | European Journal of Inorganic Chemistry, 2021 (29), 2958-2975. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject | Hydroxide complexes | es |
dc.subject | Nickel | es |
dc.subject | Palladium | es |
dc.subject | Pincer complexes | es |
dc.subject | Reaction mechanisms | es |
dc.title | Nucleophilic Nickel and Palladium Pincer Hydroxides: A Study of Their Reactions with Dimethyl Carbonate and Other Non-Alkylating Organic Electrophiles | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Inorgánica | es |
dc.relation.projectID | PGC2018-095768-B-100 | es |
dc.relation.projectID | PY20_0104 | es |
dc.relation.publisherversion | https://doi.org/10.1002/ejic.202100400 | es |
dc.identifier.doi | 10.1002/ejic.202100400 | es |
dc.journaltitle | European Journal of Inorganic Chemistry | es |
dc.publication.volumen | 2021 | es |
dc.publication.issue | 29 | es |
dc.publication.initialPage | 2958 | es |
dc.publication.endPage | 2975 | es |
dc.contributor.funder | Agencia Estatal de Investigación. España | es |
dc.contributor.funder | Junta de Andalucía | es |