Reactions of Dinitrogen

11 Reactions of Dinitrogen and Carbon Dioxide whidi are Promoted by Transition-metal Compounds 

Fixation and activation of Ng, COg, CO, and Hg by magnesium in the presence of a transition-metal compound have been reviewed.  

181 Newton, J. R. Postgate, and C. Rodriguez-Barrueco, Recent Devdopments in Nitrogen Fixation Academic Press, London, 1977 J. Chatt, J. R. Dilworth, and R. Richards, Chem. Rev., 1978, 78, 589. 

CR R )(PMe2Ph)3], which also afford hydrazine as the major product when treated with Alkylation, acetylation, and aroylation reactions of 

Hydrolysis of [CoH(NaXPPh3)s] fiives hydrazine and a small amount of ammonia.  

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Cobaltilll) nitrate Co(N03)3 has been prepared by the reaction of dinitrogen pentoxide with cobalt(III) fluoride. 

Copper acetate, ferrous acetate, silver acetate [563-63-3] basic aluminum acetate, nickel acetate [373-02-4] cobalt acetate, and other acetate salts have been reported to furnish anhydride when heated. In principle, these acetates could be obtained from low concentration acetic acid. CompHcations of soHds processing and the scarcity of knowledge about these thermolyses make industrial development of this process expensive. In the eady 1930s, Soviet investigators discovered the reaction of dinitrogen tetroxide [10544-72-6] and sodium acetate [127-09-3] to form anhydride ... 

Paragraphs to be consulted regarding the dangerous reactions of dinitrogen tetroxide... 

The reaction of dinitrogen pentoxide with acetaldehyde at -196°C is very dangerous when it is carried out without using any solvent. The danger comes from the instability of the compound formed ... 

A reaction of dinitrogen tetroxide with acetonitrile in the presence of indium was carried out. The technician wanted to accelerate the process by stirring the medium, causing ils detonation. This accident was put down to the vioient oxidation of the acetonitrile accumulated, by nitrogen oxide catalysed by indium. 

The reaction of a-nitroalkenes with nitrogen dioxide or its dimer, dinitrogen tetroxide, has been used to synthesize polynitroalkanes. Thus, the reaction of dinitrogen tetroxide with 2,3-dinitro-2-butene (6) and 3,4-dinitro-3-hexene is reported to yield 2,2,3,3-tetranitrobutane (7, 25 %) and 3,3,4,4-tetranitrohexane (32 %) respectively. ... 

The Ponzio reaction provides a useful route to gem-dinitro compounds and involves treating oximes with a solution of nitrogen dioxide or its dimer in diethyl ether or a chlorinated solvent. The Ponzio reaction works best for aromatic oximes where the synthesis of many substituted aryldinitromethanes have been reported. Compound (56), an isomer of TNT, is formed from the reaction of dinitrogen tetroxide with the oxime of benzaldehyde (55) followed by mononitration of the aromatic ring with mixed acid. Yields are usually much lower for aliphatic aldoximes and ketoximes. " The parent carbonyl compound of the oxime is usually the major by-product in these reactions. 

The reaction of dinitrogen pentoxide with primary aliphatic nitramines and amines leads to deamination and the formation of a nitrate ester as the major product. Consequently, dinitrogen pentoxide cannot be used for the synthesis of primary nitramines. In contrast, both primary and secondary arylamines undergo efficient A-nitration with dinitrogen pentoxide in chlorinated solvents. ... 

Millar and co-workers studied the reaction of dinitrogen pentoxide in chlorinated solvents with a number of different A-substituted aziridines and found that reactions are highly dependent on the nature of the A-substituent on the aziridine nitrogen (Table 5.9). A-Alkylaziridines give good yields of 1,2-nitramine-nitrate product (Table 5.9, Entry 1). These... 

Two routes are feasible for the industrial synthesis of dinitrogen pentoxide and both are economically dependent on the cost of electricity. The reaction of dinitrogen tetroxide with ozone (Equation 9.3) was initially reported by Guye and latter by Harris and co-workers. This was later exploited and developed into an industrially useful process by chemists at the Defence and Evaluation Research Agency (DERA) in the It is mainly due to the... 

Ini, C. C., and B. J. Finlayson-Pitts, Reactions of Dinitrogen Pentoxide and Nitrogen Dioxide with l-Palmitoyl-2-Oleoyl-s -Glycero-3-Phosphocholine, Lipids, 26, 306-314 (1991). 

Let us examine the decomposition reaction of dinitrogen pentoxide, N2O5, at 30°C. N205(g) 2N02(g) + 1/202(9)... 

Reaction of methyl bicyck>[1.1 O]butane-l-carboxylate with dinitrogen tetroxidc gave methyl 1,3-dinitrocyclobutane-l-carboxylate (18a) as a mixture of the cis- and frans-isomers in only 17% yield. Similarly, the reaction of dinitrogen tetroxide with the corresponding ethyl ester gave the corresponding isomeric ethyl ester 18b in only 40% yield.33... 

Anhydrous chromium(III) nitrate may be prepared by the reaction of dinitrogen pentoxide with chromium carbonyl in dry carbon tetrachloride.800 The product has rather low thermal stability, is involatile and decomposition begins at 60 °C. 

The first isolation of nitrosonium ion 221 as a distinct species was in the reaction of dinitrogen trioxide and dinitrogen tetroxide with boron trifluoride531 [Eqs. (4.149) and (4.150)]. 

Two studies on the mechanism of formation of hydrazido(2-) complexes by the reaction of dinitrogen complexes with acids have been reported (186,187). The salient features of these two mechanisms (one found in methanol, the other in tetrahydrofuran), will be discussed separately, and then compared. 

The increased basicity of a ligand when coordinated to the heavier metals in a transition metal triad has been appreciated for some time (311). This is manifest in (1) the rate of alkylation of alkyldiazenido complexes (kw/kMo = 5.4) (93), and (2) the rate of formation of hydra-zido(2-) complexes by the reaction of dinitrogen complexes with acid, in methanol ( w// Mo = 9.2 x 102) (186), and in tetrahydrofuran (kw/ kMo = 29-85, dependent upon the acid and substrate employed) (187). Clearly the electron-releasing capability of the metal has conflicting influences on the rate, but as in Section VI,El the basicity influence dominates. 

The reaction of dinitrogen with irradiated inorganic materials has been also tested for reactions different from the photofixation of dinitrogen. In this way, Lichtin et al. (1984) have reported that a mixture of N2 and C02 exposed on irradiated transition metal oxides of the VIII group produced a substantial number of amino-acids someones of which are considered essential in the biochemistry of humans. 

Scheme 2 Some reactions of dinitrogen complexes of rhenium(l)...

To avoid any such back reaction of dinitrogen tetroxide with nitronium perchlorate, we decided to carry out our study under vacuum, with... 

Mori reported that Ti-N complexes obtained from N2 fixation could be utilized to prepare aniline derivatives via the Pd-catalyzed cross-coupling [115]. The complexes obtained from the reaction of dinitrogen with a mixture of lithium metal, Ti(Oi-Pr)4, and TMSCl served as an effective ammonia equivalent to produce the desired aniline derivative after workup, Eq. (136). Thus, with this system, the removal of any nitrogen protecting group was obviated. 

While the latter reactions are no longer used for nitrogen fixation, the reaction of dinitrogen with dihydrogen to form ammonia is among the most important industrial processes. The alkaline-earth metals react readily with dinitrogen at elevated temperatures to form nitrides lithium reacts even at room temperature with dinitrogen. 

The reaction of dinitrogen tetroxide with alkenes generally gives 1,2-dinitro compounds, fi-ni-tro nitrites and /5-nitro nitrates, often as mixtures, by a radical mechanism (Section 7.2.1.7). However, a /5-nitroso nitrate was obtained by the heterolysis (NO NOf) of dinitrogen tetroxide and ionic addition to 2,3-dimethyl-2-butene71. 

The reaction of dinitrogen pentoxide with ( )- and (Z)-2-butenes and ( )-l,2-diphenyl-ethylene afforded the corresponding nitro nitrates predominantly by syn addition114. 

This is surprising, since the reaction of dinitrogen tetroxide with (E)-, 2-diphenylethylene in diethyl ether produced a 3 2 mixture of diastereomeric l,2-dinitro-l,2-diphenylethanes134 The reaction of 2-cholestene with dinitrogen tetroxide/iodine afforded 2/ -iodo-3a-nitro-5oi-chole-stane, this was also the product obtained by the addition of nitryl iodide (see previous section). 

The reaction of dinitrogen tetroxide/iodine gave l-iodo-2-nitrocyclopentane carboxylic acid as the major product (57% yield, undetermined configuration), precursor of the naturally occurring l-amino-2-nitrocyclopentane carboxylic acid135. 

For example, the reaction of dinitrogen and dihydrogen to form ammonia is postulated to proceed on some catalysts according to the following sequence of elementary steps ... 

Reactions of dinitrogen (N ) titanium- or group VIA-(Mo, W) coordinated species with protonic acids can yield N-protonated complexes, or free hydrazines or amines. The (h -MejCp)2TiN2 is protonated by HCl to form in 55% yields ... 

The Significance of NO, Free Radicals in the Reactions of Dinitrogen Tetroxide and Metal Nitrates... 

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