Hemichelation, a Way To Stabilize Electron-Unsaturated Complexes: The Case of T-Shaped Pd and Pt Metallacycles.
A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopi...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 47; pp. 17839 - 17853 |
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| Autores principales: | , , , , , |
| Formato: | Artículo |
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American Chemical Society
11/27/2013
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=92977778&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 92977778 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/27/2013 vid: 135 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 92977778 10.1021/ja4076327 ppf: 17839 ppct: 14 formats: tig: atl: Hemichelation, a Way To Stabilize Electron-Unsaturated Complexes: The Case of T-Shaped Pd and Pt Metallacycles. aug: au: Werlé, Christophe Bailly, Corinne Karmazin-Brelot, Lydia Le Goff, Xavier-Frédéric Ricard, Louis Djukic, Jean-Pierre affil: Institut de Chimie de Strasbourg, Université de Strasbourg, CNRS, 4 rue Blaise Pascal, F-67000 Strasbourg, France Département de Chimie, Ecole Polytechnique, CNRS, Route de Saclay, F-91128 Palaiseau cedex, France su: Metallacycles Electron research Density functionals Ligands (Chemistry) Nuclear particle research sug: subj: Metallacycles Electron research Density functionals Ligands (Chemistry) Nuclear particle research ab: A rational method of synthesis of stable neutral T-shaped 14 electron Pd and Pt complexes is proposed. It takes advantage of the ambiphilic character of the tricarbonyl(η-indenyl)chromium anion, of which the main property is to behave as a hemichelating ligand, that is a nonconventional heteroditopic ligand capable of chelating a metal center by way of covalent and noncovalent bonding, thus preserving its unsaturated valence shell. The reaction of the in situ formed tricarbonyl(η-2-methylindenyl)chromium anion with a series of Pd and Pt metallacycles afforded new air-stable and persistent synfacial heterobimetallic complexes in which the metallacycle binds the indenyl fragment via its metal in an η fashion, leaving the fourth coordination site at the chelated metal virtually vacant. The structures of eight of these novel complexes are disclosed, and their bonding features are investigated by an array of theoretical methods based on the density functional theory (NBO, EDA, ETS-NOCV, AIM, NCI region analysis). Theory shows that the formation of these unusual structures of bimetallic synfacial η-indenyl-Pd/Pt complexes is driven thermodynamically by attractive Coulombic occlusion of the fourth vacant coordination site at Pd/Pt centers by the Cr(CO) moiety. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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