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Polynuclear platinum phosphanido/phosphinito complexes: formation of P-O and P-O-P bonds through reductive coupling processes
dc.contributor.author | Ara, Irene | |
dc.contributor.author | Forniés, Juan | |
dc.contributor.author | Ibáñez, Susana | |
dc.contributor.author | Mastrorilli, Piero | |
dc.contributor.author | Todisco, Stefano | |
dc.contributor.author | Gallo, Vito | |
dc.date.accessioned | 2016-12-07T13:45:25Z | |
dc.date.available | 2016-12-07T13:45:25Z | |
dc.date.issued | 2015-11 | |
dc.identifier.citation | ARA, Irene, et al. Polynuclear platinum phosphanido/phosphinito complexes: formation of P–O and P–O–P bonds through reductive coupling processes. Dalton Transactions, 2016, vol. 45, no 5, p. 2156-2171. | ca_CA |
dc.identifier.uri | http://hdl.handle.net/10234/164940 | |
dc.description.abstract | A mixture of the asymmetric complexes of formula [(RF)2Pt(μ-Ph2PO)(μ-PPh2)Pt(μ-PPh2)2Pt(solv)(solv′)] [(1-(solv)(solv′)] (solv, solv′ = acetone, H2O, CH3CN) has been prepared by reaction of [(RF)2PtII(μ-PPh2)2PtII(μ-PPh2)2PtII(NCCH3)2] with AgClO4 in CH3CN/acetone. The lability of the Pt–solvent bonds allows the displacement of the coordinated solvent molecules by dppm or Cl− and the isolation of the tri- or hexanuclear phosphanido/phosphinito Pt(II) complexes [(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(dppm)] (2) or [NBu4]2[(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(μ-Cl)2Pt(μ-PPh2)2Pt(μ-PPh2)(μ-PPh2O)Pt(C6F5)2] (as a mixture of the two possible isomers 4a and 4b). Complex 2 reacts with AgClO4 to form the tetranuclear derivative [(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(dppm)Ag(OClO3)] (3), which displays two Pt–Ag donor–acceptor bonds. The mixture of the hexanuclear isomers 4a–4b reacts with Tl(acac) producing the acetylacetonato complex [NBu4][(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(acac)] (5) which, upon reaction with HCl, yields back the mixture of 4a–4b. The reaction of 4a–4b with PPh3 produces [NBu4][(C6F5)2Pt(μ-PPh2)(μ-PPh2O)Pt(μ-PPh2)2Pt(Cl)(PPh3)] (6) as a mixture of isomers with the chloro ligand located syn (6a) or anti (6b) to the PPh2O− group. Either the reaction of 6 with AgClO4 or the treatment of 5 with HPPh3ClO4 results in the formation of the species [(C6F5)2PtII(μ-PPh2)2PtI(μ-PPh2OPPh2)PtI(PPh3)] (7) (44 VEC), which can be explained as the consequence of a PPh2O/PPh2 reductive coupling and a rearrangement of ligands in the molecule generating a Pt(II),Pt(I),Pt(I) compound. All complexes were characterised in the solid state by XRD (only one of the isomers, in the cases of 4 and 6) and in solution by NMR spectroscopy. | ca_CA |
dc.description.sponsorShip | This work was supported by Ministerio de Economía y Competitividad (MINECO)/FEDER (project number CTQ2012-35251) and the Gobierno de Aragón and Fondo Social Europeo (Grupo Consolidado E21: Química Inorgánica y de los Compuestos Organometálicos). We express our grateful acknowledgement to the Politecnico di Bari for its financial support. Finally, we thank Dr Consuelo Fortuño for her helpful discussions. | ca_CA |
dc.format.extent | 15 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | The Royal Society of Chemistry | ca_CA |
dc.relation.isPartOf | Dalton Trans., 2016, 45 | ca_CA |
dc.rights | © The Royal Society of Chemistry 2016 | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | * |
dc.subject | Platinum | ca_CA |
dc.subject | Pt complexes | ca_CA |
dc.subject | Phosphanides | ca_CA |
dc.subject | Reductive couplings | ca_CA |
dc.title | Polynuclear platinum phosphanido/phosphinito complexes: formation of P-O and P-O-P bonds through reductive coupling processes | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1039/C5DT02593A | |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://pubs.rsc.org/en/content/articlehtml/2016/dt/c5dt02593a | ca_CA |
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