A mechanistic study of the samarium(II)-mediated reduction of aryl nitro compounds to the corresponding crylamines. The crystal structures of [Sm[N(SiMe(3))(2)](2)(thf)](2)(mu(2)-O) and [(Me(3)Si)(2)N](2)Sm(thf)(mu-PhNNPh)Sm[N(SiMe(3))(2)](2)

Erik D Brady; David L Clark; D Webster Keogh; Brian L Scott; John G Watkin

doi:10.1021/ja0168918

A mechanistic study of the samarium(II)-mediated reduction of aryl nitro compounds to the corresponding crylamines. The crystal structures of [Sm[N(SiMe(3))(2)](2)(thf)](2)(mu(2)-O) and [(Me(3)Si)(2)N](2)Sm(thf)(mu-PhNNPh)Sm[N(SiMe(3))(2)](2)

J Am Chem Soc. 2002 Jun 19;124(24):7007-15. doi: 10.1021/ja0168918.

Authors

Erik D Brady¹, David L Clark, D Webster Keogh, Brian L Scott, John G Watkin

Affiliation

¹ Contribution from the Chemistry Division, Nuclear Materials Technology Division, and the G.T. Seaborg Institute for Transactinium Science, Los Alamos National Laboratory, Los Alamos, New Mexico 87545.

PMID: 12059224
DOI: 10.1021/ja0168918

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.