Nitrato derivatives

The nitrato-derivative of the series is unknown. Treatment of palladous nitrate with ammonia does not yield the corresponding nitrato-derivative, which appears to be unstable. A liquid is, however, obtained by treating the chloro-derivative with silver nitrate, but on evaporation a brown substance separates which detonates on heating. 

Photolysis of a iV-nitrosamide under an inert atmosphere and in the presence of oxygen has previously been demonstrated to functionalize specifically the 5-position with respect to the amide nitrogen atom, leading to the formation of the corresponding C-nitroso- and C-nitrato-derivatives respectively. Two nitrosamides, -nitroso-iV-acetyldehydroabietylamine and N-nitroso-AT-methyl-... 

Trahanovsky, W. S. et al., J. Amer. Chem. Soc., 1971, 93, 5257 Although several other l-azido-2-nitrato-alkanes appeared thermally stable, the acenaphthane derivative exploded violently on heating (probably dining analytical combustion). 

Aquo - derivatives of nitrato - pentammino - salts are known. For example, nitrato-aquo-tetrammino-cobaltic nitrate, [Co(NH3)4 (H20)(X03)](X03)2, is prepared from carbonato-tetranunino-eobaltic nitrate, [Co(XH3).1(C03)]N03,a by treating it in aqueous solution with concentrated nitric acid, when the aquo-salt is precipitated. 

Nitrato-salts of the same type as the chloro- or bromo-salts have also been prepared.1 The salts of the aeido-nitroso-tetrammino-ruthenium type are typical aeido-ammino-derivatives. 

The fodo-derivative, [Pt(NH3)2Is], separates as a mierocrystalline yellow powder on mixing aqueous potassium iodide and the nitrato-compound. It is only slightly soluble ill water. 

Zinc and cadmium nitrato complexes of the 2,6-diacetylpyridine derivatives (37) have been prepared, and reveal a variety of nitrate bonding modes.351... 

A somewhat surprising group of coordination compounds consists of the volatile heavy metal nitrates, such as those of copper, zinc, mercury, titanium, zirconium and hafnium. The structures of some of these, in the gaseous state, have been determined thus Cu(N03)2 contains two bidentate, almost planar, staggered nitrato groups. Some derivatives of metal nitrates have also been found to be volatile for example, Fe(N03)3 N204 and Al(N03)3 2MeCN.39... 

The oxygenation of the related Co system BCo(DH)2(NO) where DH = dimethylglyoximate, B = pyridine derivatives, PPh3 and N-methylimidazole, has been studied by Trogler and Marzilli (214). The main difference from the study by Basolo is the observation of a mixture of products. An O-bonded nitrato compound is obtained as the major product in this reaction with the expected nitro species giving less than 50% of the product mixture. The authors were unable to explain the occurrence of the product mixture, or elucidate the mechanism of O-bonded NOa formation. It does seem clear, however, that electrophilic attack by 02 at NO- is the key step in the reaction. In the absence of added bases, the reactivity of the nitrosyl should be diminished with respect to electrophilic attack, and it is found that only nitro products are obtained (214). 

On the basis of these observations and conclusions it was suggested that the cobalt complexes described above might follow a related pathway. Here, however, it can be argued that the presence of base in, e.g. the reactions of Co(dmgH)2NO, leads initially to the quantitative formation of Co,(dmgH)2(NO)B. In this case attack of 02 leads first to the peroxy compounds and then, because of the absence of a suitable NO+ compound, rearrangement occurs to give the nitrito derivative. Clearly whether or not nitro or nitrato compounds are produced would depend on the concentration of base B. In some cases it is possible to obtain mixtures of such products. These oxidations are also observed for other metals, e.g. equations (37) and (38). 

The IR spectrum of [Ni(H2L)(N03)](N03), where H2L = ethylenedia-mine dioxime derivative of 3-carene, shows that the nitrato ligand is bidentate, with H2L coordinated as an N4 ligand.415 IR bands due to nitrato ligands in cis- and tra w-Pt(amine)2(N03)2, where amine = RNH2 (R = Me, Et, nPr, nBu, Pr, Bu, secBu, lBu) or Me2NH, were all consistent with unidentate coordination.416... 

Although several other l-azido-2-nitrato-alkanes appeared thermally stable, the acenaphthane derivative exploded violently on heating (probably during analytical combustion). 

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