A Mechanistic Study of the Samarium(II)-Mediated Reduction of Aryl Nitro Compounds to the Corresponding Arylamines. The Crystal Structures of {Sm[N(SiMe3)2]2(thf)}2(μ2-O) and [(Me3Si)2N]2Sm(thf)(μ-PhNNPh)Sm[N(SiMe3)2]2
Journal of the American Chemical Society2002Vol. 124(24), pp. 7007–7015
Citations Over TimeTop 22% of 2002 papers
Abstract
Treatment of nitrobenzene and other various nitroarenes with 6 equiv of samarium(II) under strictly anhydrous conditions allows for the isolation of aniline or the corresponding arylamine. Reducing the number of samarium(II) equivalents allows for the isolation of intermediate species, e.g., azoarenes or hydrazines. Use of Sm[N(SiMe(3))(2)](2), in place of the typically used SmI(2), has allowed for the detailed examination of the aqueous and nonaqueous species formed in this reduction and has been instrumental in delineation of the stepwise reaction mechanism. This is the first time that the reaction intermediates of an organic reaction mediated by samarium(II) have been isolated and analyzed by (1)H NMR and X-ray crystallography.
Related Papers
- → Comparative evaluation of electroreduction of nitrobenzene and m-dinitrobenzene on Ti/TiO2 electrodes in H2SO4(1994)7 cited
- → Arylation by aromatic nitro compounds at high temperatures. III. Reactions of nitrobenzene with aromatic fluorine derivatives(1967)12 cited
- → Arylation by aromatic nitro ompounds at high temperatures. VI. Reactions of nitrobenzene and nitrobenzene-d5 with pyridine(1970)6 cited
- Comparisons of the structure, stability and electron distribution of nitrobenzenes and nitro-sym-triazines(1986)
- → Catalytic Reduction of Aromatic Nitro Compounds in the Presence of Water. III(1963)