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| DC Field | Value | Language |
|---|---|---|
| dc.contributor.author | Fornies, J. | en |
| dc.contributor.author | Fuertes, S. | en |
| dc.contributor.author | Larraz, C. | en |
| dc.contributor.author | Martin, A. | en |
| dc.contributor.author | Sicilia, V. | en |
| dc.contributor.author | Tsipis, A. C. | en |
| dc.date.accessioned | 2015-11-24T16:49:01Z | - |
| dc.date.available | 2015-11-24T16:49:01Z | - |
| dc.identifier.uri | https://olympias.lib.uoi.gr/jspui/handle/123456789/9411 | - |
| dc.rights | Default Licence | - |
| 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 | en |
| heal.type | journalArticle | - |
| heal.type.en | Journal article | en |
| heal.type.el | Άρθρο Περιοδικού | el |
| heal.identifier.primary | 10.1021/om201036z | - |
| heal.identifier.secondary | http://pubs.acs.org/doi/abs/10.1021/om201036z | - |
| heal.language | en | - |
| heal.access | campus | - |
| heal.recordProvider | Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας | el |
| heal.publicationDate | 2012 | - |
| heal.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]ClO4 and [K(H2O)][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 Cbzq 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 Cbzq, yielding the [(RNC)(bzq)(μ2-η1,η1-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(μ2-η1,η1-CN)Pt(bzq)(CN)]. | en |
| heal.publisher | American Chemical Society | en |
| heal.journalName | Organometallics | en |
| heal.journalType | peer reviewed | - |
| heal.fullTextAvailability | TRUE | - |
| Appears in Collections: | Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά). ΧΗΜ | |
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