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Title: | Kinetico-mechanistic studies on intramolecular C-X bond activation (X = Br, Cl) of amino-imino ligands on Pt(II) compounds. Prevalence of a concerted mechanism in nonpolar, polar and ionic liquid media |
Author: | Calvet Pallàs, Maria Teresa Crespo Vicente, Margarita Ma. Font Bardia, Ma. Mercedes Jansat, Sussana Martínez López, Manuel, 1957- |
Keywords: | Hidrocarburs Lligands Estructura molecular Dissolvents Hydrocarbons Ligands Molecular structure Solvents |
Issue Date: | 2012 |
Publisher: | American Chemical Society |
Abstract: | The C–Br and C–Cl oxidative addition reactions of molecules containing a set of {N-amino,N-imino} chelating donor groups (2-X,6-YC6H4CHNCH2CH2NMe2, X = Br, Cl; Y = Cl, H) attached to a {PtII(Ar)2} (Ar = Ph, 4-MeC6H4) have been studied. The Pt(IV) complexes formed, [PtAr2X{2-YCC5H3CH═NCH2CH2NMe2}], containing a metalated tridentate [C,N,N′] ligand have been fully characterized by the usual techniques, and the X-ray crystal structure of the complex with Ar = 4-MeC6H4 and X =Y = Cl has been determined. Monitoring of the reactions at varying temperatures and pressures and in different solvents agrees with a mechanism that involves the preliminary decoordination of the N-amino donor from the ligand to produce a three-coordinated intermediate. This evolves, via a concerted C–X bond activation, to form a second pentacoordinated intermediate species that, on coordination of the N-amino donor, produces the final complex. The kinetico-mechanistic parameters measured indicate that the concerted character of the process is maintained from nonpolar (xylene and toluene) to polar (acetone) and ionic liquid ((Bmin(NTf2)) media. Furthermore, the ΔV⧧ values measured indicate that, for the (2,6-Cl)C6H3CH═NCH2CH2NMe2 ligand, the existence of hydrogen bonding within the metalating molecule is a determinant for the acceleration observed. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1021/om300374f |
It is part of: | Organometallics, 2012, vol. 31, num.11, p. 4367-4373 |
URI: | http://hdl.handle.net/2445/210360 |
Related resource: | https://doi.org/10.1021/om300374f |
ISSN: | 0276-7333 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada) |
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