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http://hdl.handle.net/2445/164837
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DC Field | Value | Language |
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dc.contributor.author | Aullón López, Gabriel | - |
dc.contributor.author | Crespo Vicente, Margarita Ma. | - |
dc.contributor.author | Font Bardia, Ma. Mercedes | - |
dc.contributor.author | Jover Modrego, Jesús | - |
dc.contributor.author | Martínez López, Manuel, 1957- | - |
dc.contributor.author | Pike, J. | - |
dc.date.accessioned | 2020-06-08T17:45:18Z | - |
dc.date.available | 2020-06-08T17:45:18Z | - |
dc.date.issued | 2015 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/2445/164837 | - |
dc.description.abstract | The metalation reactions between [Pt2(4-MeC6H4)4(μ-SEt2)2] and 2-X,6-FC6H3CHvNCH2CH2NMe2 (X = Br, Cl) have been studied. In all cases, seven-membered platinacycles are formed in a process that involves an initial reductive elimination from cyclometallated PtIV intermediate compounds, [PtX(4-CH3C6H4)2(ArCHvNCH2CH2NMe2)] (X = Br, Cl), followed by isomerization of the resulting PtII complexes and a final cyclometallation step. For the process with X = Br, the final seven-membered platinacycle and two intermediates, isolated under the conditions implemented from parallel kinetic studies, have been characterized by XRD. Contrary to previous results for the parent non-fluorinated imine 2-BrC6H4CHvNCH2CH2NMe2 the presence of a fluoro substituent prevents the formation of the more stable five-membered platinacycle. Temperature and pressure dependent kinetico-mechanistic and DFT studies indicate that the final cyclometallation step is strongly influenced by the nature of the spectator halido ligand, the overall reaction being much faster for X = Cl. The same DFT study conducted on the previously studied systems with imine 2-BrC6H4CHvNCH2CH2NMe2 indicates that, when possible, fivemembered platinacycles are kinetically preferred for X = Br, while the presence of Cl as a spectator halido ligand leads to a preferential faster formation of seven-membered analogues. | - |
dc.format.extent | 35 p. | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | - |
dc.publisher | Royal Society of Chemistry | - |
dc.relation.isformatof | Versió postprint del document publicat a: https://doi.org/10.1039/C5DT02657A | - |
dc.relation.ispartof | Dalton Transactions, 2015, vol. 44, num. 41, p. 17968-17979 | - |
dc.relation.uri | https://doi.org/10.1039/C5DT02657A | - |
dc.rights | (c) Aullón López, Gabriel et al., 2015 | - |
dc.source | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) | - |
dc.subject.classification | Complexos metàl·lics | - |
dc.subject.classification | Lligands | - |
dc.subject.classification | Cinètica química | - |
dc.subject.other | Metal complexes | - |
dc.subject.other | Ligands | - |
dc.subject.other | Chemical kinetics | - |
dc.title | A combined kinetico-mechanistic and computational study on the competitive formation of seven- versus five-membered platinacycles; the relevance of spectator halide ligands | - |
dc.type | info:eu-repo/semantics/article | - |
dc.type | info:eu-repo/semantics/acceptedVersion | - |
dc.identifier.idgrec | 654791 | - |
dc.date.updated | 2020-06-08T17:45:19Z | - |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | - |
Appears in Collections: | Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
Files in This Item:
File | Description | Size | Format | |
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654791.pdf | 2.29 MB | Adobe PDF | View/Open |
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