The effect of the chloride countercation on the mechanism of the Ru-3(CO)(12)/chloride catalyzed carbonylation of nitroarenes to carbamates has been investigated. The reason for the higher activity and selectivity obtained with tetraethylammonium chloride with respect to [PPN][Cl] is due to the higher igroscopicity of the former (only when no aniline is added) and to its ability do decompose to yield triethylamine. The role of this last compound is twofold. On one hand, it accelerates the alcoholysis of the intermediately formed diarylurea. On the other, it favors a reaction pathway that consumes aniline together with nitrobenzene, thus converting a by-product into the desired product. (C) 2000 Elsevier Science B.V. All rights reserved.
Mechanistic study of the Ru-3(CO)(12)/chloride catalyzed carbonylation reactions of nitroarenes to carbamates and ureas; the role of the alkylammonium cation / F. Ragaini, S. Cenini. - In: JOURNAL OF MOLECULAR CATALYSIS. A: CHEMICAL. - ISSN 1381-1169. - 161:1-2(2000), pp. 31-38.
|Titolo:||Mechanistic study of the Ru-3(CO)(12)/chloride catalyzed carbonylation reactions of nitroarenes to carbamates and ureas; the role of the alkylammonium cation|
RAGAINI, FABIO ATTILIO CIRILLO (Primo)
CENINI, SERGIO (Ultimo)
|Parole Chiave:||Carbonylation reactions; Homogeneous catalysis; Nitrobenzene; Ruthenium; Urethane|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||2000|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1016/S1381-1169(00)00311-3|
|Appare nelle tipologie:||01 - Articolo su periodico|