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
Φόρτωση...
Ημερομηνία
Συγγραφείς
Fornies, J.
Fuertes, S.
Larraz, C.
Martin, A.
Sicilia, V.
Tsipis, A. C.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
American Chemical Society
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Organometallics
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
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)].
Περιγραφή
Λέξεις-κλειδιά
Θεματική κατηγορία
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Σύνδεσμος
http://pubs.acs.org/doi/abs/10.1021/om201036z
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας