Reduction of nitrobenzene by dodecacarbonyl tri-iron under triphase conditions
TL;DR: In this article, the reduction of nitrobenzene to aniline by Fe3(CO)12 under triphase conditions has been investigated and the efficiency of the polymer-supported phase transfer agents compared.
About: This article is published in Journal of Molecular Catalysis.The article was published on 1989-07-01. It has received 9 citations till now. The article focuses on the topics: Nitrobenzene & Aniline.
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TL;DR: The use of CO as a reductant had been in the past confined to few reactions, but its use in organic synthesis, especially in the reductive carbonylation of nitro aromatics and the oxidative carbonylations of aromatic amines, has increased dramatically as mentioned in this paper.
Abstract: Although the use of CO as a reductant had been in the past confined to few reactions, its use in organic synthesis, especially in the reductive carbonylation of nitro aromatics and the oxidative carbonylation of aromatic amines, has increased dramatically. Since the discovery of CO-induced reduction of nitro groups, there has been a wide spread increase of interest in the application and mechanistic understanding of this reaction. In a major review published in 1988 it was noted, that in practice no studies of the mechanism of N-carbonylation of aromatic nitro compounds with alcohols leading to carbamates have been carried out. This review clearly shows a major change since that publication. Indeed, metal-catalyzed reductive carbonylation of nitro aromatics using CO as reducing agent has been in the past 10 years the subject of intense investigation both in academia and in the chemical industry. Several articles and reviews have covered the subject up to the late 1980s. The authors will concentrate on more recent literature, but sometimes older data will be used to establish an understanding of these reactions. 127 refs.
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TL;DR: In this article, the phase-transfer-catalyzed reaction of Fe3(CO)12 with OH- affords the radical anion cluster [Fe3[CO]•- and not [HFe3•CO]−.
25 citations
TL;DR: Aromatic nitroderivatives e.g. nitrobenzene can be carbonylatively reduced with CO in water-methanol media, at 120-150°C and 10-15 MPa pressure.
15 citations
6 citations
TL;DR: In this paper, the authors define a set of coordinats avec des coordinats hapto: reactivite des complexes de fer carbonyle ou non, and define the coordinats as:
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308 citations
TL;DR: In this paper, the synthesis and characterization of catalysts derived from Fe(CO)5, Fe,(C0)9, and Fe3(C 0)12 supported on 7-AI2O3 are described.
Abstract: The syntheses and characterization of catalysts derived from Fe(CO)5, Fe,(C0)9, and Fe3(C0)12 supported on 7-AI2O3 are described. The temperature-programmed decomposition (TPDE) spectra of the Fe(CO), and Fe3(CO)12 catalysts are different, suggesting that the nuclearity of the precursor complex can influence the chemistry of supported complexes. Fe2(C0)9 dry mixed with A1203 probably undergoes some decomposition to Fe(CO)5 and Fe3(C0)12 prior to bonding to the support. Activation at low temperatures (51 50 "C) leads primarily to the formation of zerovalent subcarbonyl species, some of which are reversibly formed. Activation at high temperatures (2300 "C) leads to extensive oxidation of the Fe by reaction with the surface hydroxyl groups of the A1203 and loss of reversibility. Compared to the TPDE of the bulk unsupported carbonyls, A1203 stabilizes subcarbonyl species over a broad range of temperatures and inhibits their migration, preventing the formation of an Fe mirror. Chemisorption of CO indicates that catalyts derived from the iron carbonyls can be more than an order of magnitude more dispersed than catalysts synthesized by the traditional technique of impregnation with salts of Fe3+
89 citations
65 citations
TL;DR: Typical phase-transfer catalysts, such as organophilic onium salts, crown ethers, and cryptands, when immobilized on a polymer matrix retain most of their catalytic activity, thus permitting catalyst recycling by simple filtration from the reaction medium.
Abstract: Typical phase-transfer catalysts, namely organophilic onium salts, crown ethers, and cryptands, when immobilized on a polymer matrix retain most of their catalytic activity, thus permitting catalyst recycling by simple filtration from the reaction medium.
65 citations
TL;DR: In this article, the authors discuss stoichiometric organic reactions, catalytic organic reactions and organometallic synthesis using phase-transfer catalysis, and discuss the use of halides with quaternary ammonium halides functioning as catalysts.
Abstract: Publisher Summary This chapter discusses stoichiometric organic reactions, catalytic organic reactions, and organometallic synthesis. One of the major developments in organic chemistry during the past 15 years has been the application of phase-transfer catalysis to synthesis. As a basis for discussing the concept of the liquid–liquid phase-transfer process, nucleophilic substitution reactions of halides with quaternary ammonium halides functioning as catalysts are considered in the chapter. The first experiments that were carried out in the author's laboratory on organometallic phase-transfer catalysis were concerned with the reduction of nitrobenzenes to anilines by triiron dodecacarbonyl. The reaction of halides with iron pentacarbonyl, base, and tetrabutylammonium bromide as the catalyst has been reported to give ketones and variable amounts of hydrocarbons. One of the most important metal carbonyl anions, as far as catalytic processes are concerned, is the cobalt tetracarbonyl anion, Co(CO)4−. The chapter describes crown ether-catalyzed generation of the Co(CO)4− ion in ether or hydrocarbon solvents. The carbonylation of halides to carboxylic acids, catalyzed by Co2(CO)8, is a transformation of genuine synthetic utility. Even certain phase-transfer catalysts can be carbonylated to carboxylic acids by acetylcobalt tetracarbonyl. Alcohols can be dehydrogenated to carbonyl compounds by exposure to a catalytic amount of a rhodium complex under phase-transfer conditions. The formation of dihalocarbene is one of the most useful phase-transfer processes developed in organic chemistry. Chromium tricarbonyl complexes of arylacetic esters can be alkylated by the use of phase-transfer catalysis or sodium hydride in N,N-dimethylformamide.
53 citations