dc.creator | Somerville, Rosie J. | es |
dc.creator | Borys, Andryj M. | es |
dc.creator | Pérez Jiménez, Marina | es |
dc.creator | Nova, Ainara | es |
dc.creator | Balcells, David | es |
dc.creator | Malaspina, Lorraine A. | es |
dc.creator | Grabowsky, Simon | es |
dc.creator | Carmona Guzmán, Ernesto | es |
dc.creator | Hevia, Eva | es |
dc.creator | Campos, Jesús | es |
dc.date.accessioned | 2022-10-13T16:13:57Z | |
dc.date.available | 2022-10-13T16:13:57Z | |
dc.date.issued | 2022 | |
dc.identifier.citation | Somerville, R.J., Borys, A.M., Pérez Jiménez, M., Nova, A., Balcells, D., Malaspina, L.A.,...,Campos, J. (2022). Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: revealing the hidden C6H4 ligand. Chemical Science, 13, 5268. https://doi.org/10.1039/d2sc01244h. | |
dc.identifier.issn | 2041-6520 | es |
dc.identifier.issn | 2041-6539 | es |
dc.identifier.uri | https://hdl.handle.net/11441/137887 | |
dc.description.abstract | More than four decades ago, a complex identified as the planar homoleptic lithium nickelate “Li3NiPh3(solv)3” was reported by Taube and co-workers. This and subsequent reports involving this complex have lain dormant since; however, the absence of an X-ray diffraction structure leaves questions as to the nature of the Ni-PhLi bonding and the coordination geometry at Ni. By systematically evaluating the reactivity of Ni(COD)2 with PhLi under different conditions, we have found that this classical molecule is instead a unique octanuclear complex, [{Li3(solv)2Ph3Ni}2(μ-η2:η2-C6H4)] (5). This is supported by X-ray crystallography and solution-state NMR studies. A theoretical bonding analysis from NBO, QTAIM, and ELI perspectives reveals extreme back-bonding to the bridging C6H4 ligand resulting in dimetallabicyclobutane character, the lack of a Ni-Ni bond, and pronounced σ-bonding between the phenyl carbanions and nickel, including a weak σC-Li → sNi interaction with the C-Li bond acting as a σ-donor. Employing PhNa led to the isolation of [Na2(solv)3Ph2NiCOD]2 (7) and [Na2(solv)3Ph2(NaC8H11)Ni(COD)]2 (8), which lack the benzyne-derived ligand. These findings provide new insights into the synthesis, structure, bonding and reactivity of heterobimetallic nickelates, whose prevalence in organonickel chemistry and catalysis is likely greater than previously believed. | es |
dc.description.sponsorship | European Research Council 756575 | es |
dc.description.sponsorship | Ministerio de Ciencia e Innovación PID2019-110856GA-I00 | es |
dc.description.sponsorship | Junta de Andalucía P18-FR-4688 | es |
dc.description.sponsorship | Norwegian Research Council 262695 | es |
dc.description.sponsorship | Norwegian Metacenter for Computational Science nn4654k | es |
dc.description.sponsorship | Swiss National Science Foundation (SNSF) 206021_177033 | es |
dc.format | application/pdf | es |
dc.format.extent | 9 p. | es |
dc.language.iso | eng | es |
dc.publisher | Royal Society of Chemistry | es |
dc.relation.ispartof | Chemical Science, 13, 5268. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: revealing the hidden C6H4 ligand | 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 | 756575 | es |
dc.relation.projectID | PID2019-110856GA-I00 | es |
dc.relation.projectID | P18-FR-4688 | es |
dc.relation.projectID | 262695 | es |
dc.relation.projectID | nn4654k | es |
dc.relation.projectID | 206021_177033 | es |
dc.relation.publisherversion | https://doi.org/10.1039/d2sc01244h | es |
dc.identifier.doi | 10.1039/d2sc01244h | es |
dc.journaltitle | Chemical Science | es |
dc.publication.volumen | 13 | es |
dc.publication.initialPage | 5268 | es |
dc.contributor.funder | European Research Council (ERC) | es |
dc.contributor.funder | Ministerio de Ciencia e Innovación (MICIN). España | es |
dc.contributor.funder | Junta de Andalucía | es |
dc.contributor.funder | Norwegian Research Council | es |
dc.contributor.funder | Norwegian Metacenter for Computational Science | es |
dc.contributor.funder | Swiss National Science Foundation (SNSF) | es |