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Title: Radical processes in the reduction of nitrobenzene promoted by iron carbonyl clusters. X-ray crystal structures of [Fe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup 2[minus]], [HFe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup [minus]], and the radical anion [Fe[sub 3](CO)[sub 11]][sup [minus]]

Abstract

Despite the apparent lower efficiency of iron-based catalysts, their use is of interest due to the comparative cost advantage of iron compared to the other metals commonly employed as catalysts for these reactions. Since little is known about the mechanism by which nitro and nitrosocompounds react with iron carbonyls, we have initiated an investigation in this area, using Fe[sub 3](CO)[sub 12] (1) and [HFe[sub 3](CO)[sub 11]][sup [minus]] (2) as starting compounds. As alkylammonium halides have been shown to be efficient cocatalysts in the related Ru[sub 3](CO)[sub 12]-catalyzed carbonylation of nitrobenzene, we have also investigated the reactivity of Fe[sub 3](CO)[sub 12] with [PPN] X salts (X = Cl[sup [minus]], Br[sup [minus]], I[sup [minus]], NCO[sup [minus]]; PPN[sup +] = (PPh[sub 3])[sub 2]N[sup +]). As described herein, this has led to the isolation of the radical anion cluster [Fe[sub 3](CO)[sub 11]][sup [minus][center dot]] (3) as PPN[sup +] or PPh[sub 4][sup +] salts, both of which have been crystallographically characterized. In this paper, we also report the results of an investigation of the reactivity of [Fe[sub 3](CO)[sub 11]][sup [minus][center dot]] with nitro and nitroso organic compounds. 50 refs., 3 figs., 4 tabs.

Authors:
; ; ;  [1]; ;  [2]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Univ. of Deleware, Newark, DE (United States)
Publication Date:
OSTI Identifier:
6583112
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 14:1; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYL RADICALS; STRUCTURAL CHEMICAL ANALYSIS; IRON COMPOUNDS; NITROBENZENE; CHEMICAL REACTIONS; REDUCTION; ORGANOMETALLIC COMPOUNDS; ANIONS; CATALYSTS; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; X-RAY DIFFRACTION; CHARGED PARTICLES; COHERENT SCATTERING; DATA; DIFFRACTION; INFORMATION; IONS; NITRO COMPOUNDS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; RADICALS; SCATTERING; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties; 400101 - Activation, Nuclear Reaction, Radiometric & Radiochemical Procedures

Citation Formats

Ragaini, F, Song, J S, Ramage, D L, Geoffroy, G L, Yap, G A.P., and Rheingold, A L. Radical processes in the reduction of nitrobenzene promoted by iron carbonyl clusters. X-ray crystal structures of [Fe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup 2[minus]], [HFe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup [minus]], and the radical anion [Fe[sub 3](CO)[sub 11]][sup [minus]]. United States: N. p., 1995. Web. doi:10.1021/om00001a054.
Ragaini, F, Song, J S, Ramage, D L, Geoffroy, G L, Yap, G A.P., & Rheingold, A L. Radical processes in the reduction of nitrobenzene promoted by iron carbonyl clusters. X-ray crystal structures of [Fe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup 2[minus]], [HFe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup [minus]], and the radical anion [Fe[sub 3](CO)[sub 11]][sup [minus]]. United States. https://doi.org/10.1021/om00001a054
Ragaini, F, Song, J S, Ramage, D L, Geoffroy, G L, Yap, G A.P., and Rheingold, A L. 1995. "Radical processes in the reduction of nitrobenzene promoted by iron carbonyl clusters. X-ray crystal structures of [Fe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup 2[minus]], [HFe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup [minus]], and the radical anion [Fe[sub 3](CO)[sub 11]][sup [minus]]". United States. https://doi.org/10.1021/om00001a054.
@article{osti_6583112,
title = {Radical processes in the reduction of nitrobenzene promoted by iron carbonyl clusters. X-ray crystal structures of [Fe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup 2[minus]], [HFe[sub 3](CO)[sub 9]([mu][sub 3]-NPh)][sup [minus]], and the radical anion [Fe[sub 3](CO)[sub 11]][sup [minus]]},
author = {Ragaini, F and Song, J S and Ramage, D L and Geoffroy, G L and Yap, G A.P. and Rheingold, A L},
abstractNote = {Despite the apparent lower efficiency of iron-based catalysts, their use is of interest due to the comparative cost advantage of iron compared to the other metals commonly employed as catalysts for these reactions. Since little is known about the mechanism by which nitro and nitrosocompounds react with iron carbonyls, we have initiated an investigation in this area, using Fe[sub 3](CO)[sub 12] (1) and [HFe[sub 3](CO)[sub 11]][sup [minus]] (2) as starting compounds. As alkylammonium halides have been shown to be efficient cocatalysts in the related Ru[sub 3](CO)[sub 12]-catalyzed carbonylation of nitrobenzene, we have also investigated the reactivity of Fe[sub 3](CO)[sub 12] with [PPN] X salts (X = Cl[sup [minus]], Br[sup [minus]], I[sup [minus]], NCO[sup [minus]]; PPN[sup +] = (PPh[sub 3])[sub 2]N[sup +]). As described herein, this has led to the isolation of the radical anion cluster [Fe[sub 3](CO)[sub 11]][sup [minus][center dot]] (3) as PPN[sup +] or PPh[sub 4][sup +] salts, both of which have been crystallographically characterized. In this paper, we also report the results of an investigation of the reactivity of [Fe[sub 3](CO)[sub 11]][sup [minus][center dot]] with nitro and nitroso organic compounds. 50 refs., 3 figs., 4 tabs.},
doi = {10.1021/om00001a054},
url = {https://www.osti.gov/biblio/6583112}, journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 14:1,
place = {United States},
year = {1995},
month = {1}
}