Identification of the monoanions and of their complexes with lithium salts possibly formed in solution during the alkylation of lithiated phenylacetonitrile dianions: Infrared spectroscopy and density functional theory calculations
| Autor: | Tekla Strzalko, Lya Wartski, Françoise Froment, J. Corset, Martine Castellà-Ventura |
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| Přispěvatelé: | Laboratoire de Dynamique Interactions et Réactivité (LADIR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS) |
| Rok vydání: | 2007 |
| Předmět: |
Acetonitriles
Alkylation Spectrophotometry Infrared Dimer Substituent Infrared spectroscopy chemistry.chemical_element Electrons Lithium Photochemistry Medicinal chemistry Analytical Chemistry chemistry.chemical_compound Isomerism [CHIM]Chemical Sciences Instrumentation Spectroscopy Atomic and Molecular Physics and Optics Solutions Monomer Models Chemical chemistry Thermodynamics Salts Density functional theory Isomerization |
| Zdroj: | Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-...] Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy [1994-..], 2007, 68 (5), pp.1340-1346. ⟨10.1016/j.saa.2007.02.014⟩ |
| ISSN: | 1386-1425 1873-3557 |
| Popis: | The carbanionic species possibly formed during the first alkylation step of phenylacetonitrile lithiated anion by CH 3 I and PhCH 2 Cl in THF–hexane solution and their complexes with the lithium salt formed have been observed by infrared spectrometry and characterized by density functional theory calculations. The spectra of alkylated phenylacetonitrile lithiated anion monomers and dimers have been identified in good agreement with calculations. The wave numbers of the vibrational modes of the alkylated species differ significantly from those of PhCHCNLi species, but do not depend appreciably on the substituent nature. Nevertheless with the methyl substituent, the isomerization equilibrium of the monomer is noticeably shifted toward the bridged (C-lithiated) species. The formation of a heterodimer at the expense of the dimer after addition of LiCl has been confirmed by experiment. |
| Databáze: | OpenAIRE |
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