The catalytic reduction of nitrobenzene at the [MoVIO2(O2CC(S)(C6H5)2)2]2− complex intercalated in a Zn(II)–Al(III) layered double hydroxide host: A kinetic model for the molybdenum–pterin binding site in nitrate reductase
✍ Scribed by Antonio Cervilla; Francisco Pérez-Pla; Antonio Ribera; Elisa Llopis; Antonio Domenech
- Publisher
- John Wiley and Sons
- Year
- 2001
- Tongue
- English
- Weight
- 475 KB
- Volume
- 33
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
The heterogeneous reduction of nitrobenzene by thiophenol catalyzed by the dianionic bis(2-sulfanyl-2,2-diphenylethanoxycarbonyl) dioxomolybdate(VI) complex, [Mo VI O 2 (O 2 CC(S)(C 6 H 5 ) 2 ) 2 ] 2Ϫ , intercalated into a Zn(II)-Al(III) layered double hydroxide host [Zn 3Ϫx Al x (OH) 6 ] xϩ , has been investigated under anaerobic conditions. Aniline was found to be the only product formed through a reaction consuming six moles of thiophenol for each mol of aniline produced. The kinetics of the system have been analyzed in detail. In excess of thiophenol, all reactions follow first-order kinetics (ln([PhNO 2 ]/[PhNO 2 ] 0 ) ϭ Ϫk app t) with the apparent rate constant k app being a complex function of both initial nitrobenzene and thiophenol concentrations, as well as linearly dependent on the amount of solid catalyst used. A mechanism for this catalytic reaction consistent with the kinetic experiments as well as the