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http://hdl.handle.net/10261/88235
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dc.contributor.author | Martínez-Salvador, Sonia | - |
dc.contributor.author | Forniés, Juan | - |
dc.contributor.author | Martín, Antonio | - |
dc.contributor.author | Menjón, Babil | - |
dc.contributor.author | Usón, Isabel | - |
dc.date.accessioned | 2013-12-05T09:08:25Z | - |
dc.date.available | 2013-12-05T09:08:25Z | - |
dc.date.issued | 2013 | - |
dc.identifier | doi: 10.1002/chem.201202648 | - |
dc.identifier | issn: 0947-6539 | - |
dc.identifier | e-issn: 1521-3765 | - |
dc.identifier.citation | Chemistry - A European Journal 19(1): 324-337 (2013) | - |
dc.identifier.uri | http://hdl.handle.net/10261/88235 | - |
dc.description.abstract | The action of moisture on the homoleptic organoplatinum(II) compound [NBu4]2[Pt(CF3)4] (1) gives rise to the carbonyl derivative [NBu4][Pt(CF3)3(CO)] (2), which is itself moisture stable. However, treatment of compound 2 with HCl(aq) results in the formation of [NBu4][cis-Pt(CF 3)2Cl(CO)] (3), which undergoes degradation of an additional CF3 group by further treatment with HCl(aq) in large excess, affording [NBu4][cis-Pt(CF3)Cl2(CO)] (4). The carbonyl derivatives 2-4 are fairly stable species, in which the CO ligand, however, can be readily extruded by reaction with trimethylamine N-oxide (ONMe3). Thus, compound 2 reacts with ONMe3 in the presence of a number of neutral or anionic ligands affording a series of singly or doubly charged derivatives with the general formulae [NBu4] [Pt(CF3)3(L)] [L=CNtBu (5), PPh3 (6), P(o-tolyl)3 (7), tht (8; tht=tetrahydrothiophene)] and [NBu 4]2[Pt(CF3)3X] [X=Cl (9), Br (10), I (11)], respectively. Compound 2 also reacts with ONMe3 and pyridin-2-thiol (C5H5NS) giving rise to the five-membered metallacyclic derivative [NBu4][Pt(CF3) 2(CF2NC5H4S-κC,κS)] (12), which can be viewed as a difluorocarbene species stabilized by intramolecular base coordination. On the other hand, treatment of compound 3 with ONMe3 in the presence of C5H5NS yields the four-membered metallacyclic compound [NBu4][Pt(CF3) 2(NC5H4S-κN,κS)] (13). The geometries of the metallacycles in compounds 12 and 13 are compared. In the absence of any additional ligand, compound 3 undergoes dimerization producing the dinuclear species [NBu4]2[{Pt(CF3) 2}2(ο-Cl)2] (14). Halide abstraction in the latter compound with AgClO4 in THF yields the solvento compound cis-[Pt(CF3)2(thf)2] (15). The highly labile character of the THF ligands in compound 15 makes this species a convenient synthon of the >cis-Pt(CF3)2> unit. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. | - |
dc.description.sponsorship | This work was supported by the Spanish MICINN (DGPTC)/FEDER (Project CTQ2008-06669-C02-01/BQU) and the Gobierno de Aragón (Grupo Consolidado E21: Química Inorgánica y de los Compuestos Organometálicos). | - |
dc.language.iso | eng | - |
dc.publisher | Wiley-VCH | - |
dc.rights | closedAccess | - |
dc.subject | Transition metals | - |
dc.subject | Platinum | - |
dc.subject | Fluorinated compounds | - |
dc.subject | C-N coupling | - |
dc.subject | C-F activation | - |
dc.title | Stepwise degradation of trifluoromethyl platinum(II) compounds | - |
dc.type | artículo | - |
dc.identifier.doi | 10.1002/chem.201202648 | - |
dc.date.updated | 2013-12-05T09:08:26Z | - |
dc.description.version | Peer Reviewed | - |
dc.contributor.funder | Ministerio de Ciencia e Innovación (España) | - |
dc.contributor.funder | European Commission | - |
dc.contributor.funder | Gobierno de Aragón | - |
dc.relation.csic | Sí | - |
dc.identifier.funder | http://dx.doi.org/10.13039/501100004837 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100000780 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100010067 | es_ES |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.grantfulltext | none | - |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | No Fulltext | - |
item.languageiso639-1 | en | - |
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