title: Anionic organic guests incorporated in zeolites: adsorption and reactivity of a Meisenheimer complex in faujasites.
abstract: Zeolites are suitable microporous hosts for positively charged organic species, but it is believed that they cannot adsorb organic anions. Pure Meisenheimer complex, derived from reduction of 2,4-dinitroaniline with NaBH4, was adsorbed inside faujasite cavities. Evidence for the internal incorporation of this negatively charged reaction intermediate comes from 1) XPS elemental analysis as a function of the depth of penetration into the particle, 2) the remarkable blue shift in lambda(max) of the Meisenheimer complex adsorbed on zeolite (ca. 470 nm) as compared to that in acetonitrile (580 nm) and 3) from the lack of reactivity with size-excluded hydride-acceptor reagents. Evidence is provided in support of an adsorption mechanism in which a neutral ion pair (alkali metal ion + Meisenheimer anion) is the actual species being adsorbed. In fact it appears that there is remarkable increase in the association constant for the ion-pair complex within the zeolite cavities as compared to DMF solution. Although this mechanism of adsorption as an ion-pair complex has precedents in the adsorption of some inorganic salts, what is novel is the notable increase in the stability and persistence of the Meisenheimer anion (a anionic reaction intermediate) as a result of zeolite inclusion. Adsorbed Meisenheimer complex exhibits much lower reactivity towards electron acceptors, oxygen, and water. Cyclic voltammetry of zeolite-modified electrodes reveals for the Meisenheimer complex adsorbed on LiY a reversible redox peak that is not observed in solution and has been interpreted as arising from site isolation and stabilisation of the electrochemically generated species.
authors.affiliation: Departament de Química, Universitat Autónoma de Barcelona, 08193 Bellaterra, Barcelona, Spain.
authors.forename: José Raul
authors.initials: JR
authors.lastname: Herance
authors.forename: Patricia
authors.initials: P
authors.lastname: Concepción
authors.forename: Antonio
authors.initials: A
authors.lastname: Doménech
authors.forename: José Luis
authors.initials: JL
authors.lastname: Bourdelande
authors.forename: Jordi
authors.initials: J
authors.lastname: Marquet
authors.forename: Hermenegildo
authors.initials: H
authors.lastname: García
mesh_terms: D000327:Adsorption; D000814:Aniline Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D000838:Anions / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D017641:Zeolites / Q000737:chemistry*
chemical_list: D000814:Aniline Compounds; D000838:Anions; D017641:Zeolites; C010934:2,4-dinitroaniline