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dc.contributor.author | Forniés, Juan | - |
dc.contributor.author | Fuertes, Sara | - |
dc.contributor.author | Larraz, Carmen | - |
dc.contributor.author | Martín, Antonio | - |
dc.contributor.author | Sicilia, Violeta | - |
dc.contributor.author | Tsipis, Athanassios C. | - |
dc.date.accessioned | 2013-01-28T09:23:08Z | - |
dc.date.available | 2013-01-28T09:23:08Z | - |
dc.date.issued | 2012 | - |
dc.identifier | doi: 10.1021/om201036z | - |
dc.identifier | issn: 0276-7333 | - |
dc.identifier | e-issn: 1520-6041 | - |
dc.identifier.citation | Organometallics 31(7): 2729-2740 (2012) | - |
dc.identifier.uri | http://hdl.handle.net/10261/65186 | - |
dc.description.abstract | Double complex salts (DCSs) of stoichiometry [Pt(bzq)(CNR) 2][Pt(bzq)(CN) 2] (bzq = 7,8-benzoquinolinate; R = tert-butyl (1), 2,6-dimethylphenyl (2), 2-naphtyl (3)) have been prepared by a metathesis reaction between [Pt(bzq)(CNR) 2]ClO 4 and [K(H 2O)][Pt(bzq)(CN) 2] in a 1:1 molar ratio under controlled temperature conditions (range: -10 to 0 °C). Compounds 1-3 have been isolated as air-stable and strongly colored solids [purple (1), orange (2), red-purple (3)]. The X-ray structure of 2 shows that it consists of ionic pairs in which the cationic and anionic square-planar Pt(II) complexes are almost parallel to each other and are connected by Pt-Pt (3.1557(4) Å) and π⋯π (3.41-3.79 Å) interactions. Energy decomposition analysis calculations on DCSs 1-3 showed relatively strong ionic-pair interactions (estimated interaction energies of -99.1, -110.0, and -108.6 kcal/mol), which are dominated by electrostatic interactions with small contributions from dispersion (π⋯π) and covalent (Pt⋯Pt) bonding interactions involving the 5d and 6p atomic orbitals of the Pt centers. Compounds 1-3 undergo a thermal (165 °C, 24 h) irreversible ligand rearrangement process in the solid state and also in solution at temperatures above 0 °C to give the neutral complexes [Pt(bzq)(CN)(CNR)] as a mixture of two possible isomers (SP-4-2 and SP-4-3). The mechanism of this process has been thoroughly explored by combined NMR and DFT studies. DFT calculations on 1-3 show that the existing Pt⋯Pt interactions block the associative attack of the Pt(II) centers by the coordinated cyanide and/or isocyanide ligands. Moreover, they support a significant transfer of electron density from the anionic to the cationic component (0.20-0.32 |e|), which renders the isocyanide ligand dissociation more feasible than that in the >free-standing> cationic [Pt(bzq)(CNR) 2] + components as well as the dissociation of the CN - in trans position to the C bzq in the anionic [Pt(bzq)(CN) 2] - component. Therefore, the first step in the ligand rearrangement pathway is the dissociation of the isocyanide in trans position to the C bzq, yielding the [(RNC)(bzq)(μ 2- η 1,η 1-CN)Pt⋯Pt(bzq)(CN)] intermediates. The rate-limiting step corresponds to the transformation of these intermediates to the neutral [Pt(bzq)(CN)(CNR)] complexes following a synchronous mechanism involving rupture of the Pt-Pt and formation of the Pt-CN bonds through transition states formulated as [(RNC)(bzq)Pt(μ 2- η 1,η 1-CN)Pt(bzq)(CN)]. © 2012 American Chemical Society. | - |
dc.description.sponsorship | This work was supported by the Spanish MICINN (Projects CTQ2008-06669-C02-01) and the Gobierno de Aragón (Grupo Consolidado: Química Inorgánica y de los Compuestos Organometálicos). | - |
dc.language.iso | eng | - |
dc.publisher | American Chemical Society | - |
dc.rights | closedAccess | - |
dc.title | Synthesis and characterization of the double salts [Pt(bzq)(CNR) 2][Pt(bzq)(CN) 2] with significant Pt⋯Pt and π⋯π interactions. Mechanistic insights into the ligand exchange process from joint experimental and dft study | - |
dc.type | artículo | - |
dc.identifier.doi | 10.1021/om201036z | - |
dc.date.updated | 2013-01-28T09:23:08Z | - |
dc.description.version | Peer Reviewed | - |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.grantfulltext | none | - |
item.openairetype | artículo | - |
item.fulltext | No Fulltext | - |
item.languageiso639-1 | en | - |
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