Nitroxyl structures

Other reactions. [l.l.lJPropellane reacts with tribromonitrosobenzene to yield a paramagnetic compound for which a bis-nitroxyl structure 43 was proposed. When the... 

Nitroxylic acid, HiNO . Yellow NajNOa formed by electrolysis NaN02 in NHj. Structure unknown free acid unknown. Nitramide, H2NNO2. A weak acid. 

Organic carbamates (RNHCOO-) commonly display monodentate coordination, as exemplified in the structurally characterized tetrahedral Co(bmc)2Cl2,438 (bmc = lV-(benzimidazoyl-2-yl)-O-methylcarbamate). An unusual route to a carbamato complex involves the reaction of Co2(CO)8 in the presence of a fourfold excess of the stable radical species tmpo, which yields the blue Co40(OOCNC9H18)6 cluster, presumably via a Co(CO)2(tmpo) intermediate, with the nitroxyl radical serving as oxidant.439... 

Similar to phenoxyl radical, the nitroxyl radical reacts rapidly with phenol Ar OH due to the low triplet repulsion in the TS of the structure >NO - - - H - - - OAr and very rapidly with amine due to a high difference in electron affinity in the TS of the structure >NO H Am. The IPM parameters for the nitroxyl radical reactions are presented in Table 18.5. 

As most of the nitroxyl spin-labelled synthetic derivatives of conjugated polyenes are light yellow crystals, the bond lengths were determined by X-ray crystallography38. The spectroscopic method used to measure the conformation is electron nuclear double resonance (ENDOR). It is beyond the scope of the present review to explain the method38 but the authors of the pertinent paper conclude that ENDOR is an accurate non-crystallographic method to determine polyene structures in solution. 

Aliphatic and aromatic nitro compounds react with all three R3M radicals to generate intermediate nitroxyl radicals of general structure R3M—O—N(O )—R. For the tin series, such radicals are implicated in the denitration of nitroalkanes25. The persistence of these radicals decreases with the nature of R in the order Me (minutes) < Et < Bu (hours)28. 

From a comparative analysis of H NMR spectra of structurally similar pairs of nitroxyl radicals of 3-imidazoline and 3-imidazoline-3-oxide, it was concluded that the nitrone group contributes to a more efficient long-range spin density delocalization in the conjugated n -system of functional groups bonded with atom C-4 (404). 

Moreover, one should mention that in spite of similar electronic structures, PBN and the isoquinoline nitrone (278) react in a different way. Under no circumstances does PBN give an oxidative methoxylation product, whereas nitrone (278) reacts readily to form a,a-dialkoxy-substituted nitroxyl radical (280) (517). Perhaps this difference might be due to the ability to form a complex with methanol in aldo-nitrones with -configuration. This seems favorable for a fast nucleophilic addition of methanol to the radical cation (RC), formed in the oxidation step. The a-methoxy nitrone (279), obtained in the initial methoxylation, has a lower oxidation potential than the initial aldo-nitrone (see Section 2.4). Its oxidation to the radical cation and subsequent reaction with methanol results in the formation of the a,a-dimethoxy-substituted nitroxyl radical (280) (Scheme 2.105). 

C-Nitroso compounds, oximes, N-hydroxyguanidines and N-hydroxyureas each contain an N-O bond and release nitric oxide (NO) or one of its redox forms under some conditions. The nitrogen atom of a C-nitroso compound formally exists in the +1 oxidation state, the same oxidation state as nitroxyl (HNO), the one-electron reduced form of N O. The nitrogen atoms of oximes, N-hydroxyguanidines, and N-hydroxyureas each formally exist in the -1 oxidation state, the same oxidation state as hydroxylamine. Consequently, the direct formation of NO (formal oxidation state = +2) from any of these species requires oxidation, one electron for a C-nitroso compound and three electrons for an oxime, N-hydroxyguanidine or N-hydroxyurea. This chapter summarizes the syntheses and properties, NO-releasing mechanisms and the known structure-activity relationships of these compounds. 

The 5,6-dihydropyrimidine-6-yl radicals discussed above behave, in their reactions with nitrobenzenes, like the simpler radicals CH2OH and CH(al-kyl)Oalkyl do, i.e. they react exclusively by addition to give nitroxyl radicals and uncatalyzed heterolysis is not observed (khs < 10 s ). If, however, a methyl group is introduced at C(6) (= CJ of the pyrimidine-6-yl radical, the corresponding nitroxyl radicals heterolyze with rate constants at 20 °C of 10 to 5 X 10 s depending on the structure of the pyrimidine and of the nitrobenzene (Eq. 16). This SnI type reaction is characterized by activation enthalpies of 30-40 kJ mol and activation entropies of — 89 to — 7 Jmol K (entropy control) [27]. The rate-enhancing effect of the methyl group is, of course, due to... 

A report was concerned with the ability of nitroxyl radicals, such as TEMPO and other related structures, to act as catalysts in the asymmetric oxidation of alcohols. Cyclic voltammetry was used to measure the oxidation potentials of the nitroxyl... 

To obtain semiconductors with magnetic properties, Fujiwara et al. (2003) developed several donor molecules containing a stable oxyl radical moiety based on the n-extended TTF framework. The TTF framework is too small to overcome the steric hindrance of the bulky nitroxyl radical and to accomplish strong intermolecular interaction indispensable for any electric conductivity. For this reason, a larger molecule was constructed and its cation-radical perchlorate was electrochemically prepared. This salt was obtained as black microcrystals of nonstoichiomteric ratio equal to 1 0.64. Being a semiconductor, the salt also manifests magnetic properties its structure is depicted in Scheme 8.13. 

The recent TUPAC Compendium of Chemical Terminology—The Gold Book recommends that the name of compounds having the structure R2N—O" R2N +—0 is more appropriately that of aminoxyl radicals . The synonymous terms nitroxyl radical or nitroxide are accordingly not desirable, even though quite popular in various fields of science and technology. This chapter follows a previous chapter of the series and, for this historical reason, retains the old terminology of the compounds in the title, but this use will be discontinued from now on in the text. 

The 1,3,2-dioxazolidinyl radical (39) gives an ESR spectrum with a p-factor = 2.0046, n = 1.600 mT, a = 0.250 mT. The aminyl structure of the radical is confirmed by p-factor and hyperfine coupling constant Un which are similar to those for other known aminyl radicals and considerably different from those for isomeric nitroxyl radicals RO(R)NO <89izvi8l9>. 

The first clues that compounds of structure I might be involved in nitrosamine-forming reactions came during the study of tertiary amine nitrosations. Smith and Loeppky had proposed ( ) in their detailed, classical investigation of the mechanism of this reaction that the first steps involve nitrosammonium ion formation followed by elimination of nitroxyl (HNO). The resulting immonium ion was postulated to hydrolyze to the secondary amine, which reacted with nitrosating agent to form the observed product. These mechanistic proposals are summarized in Fig. 2a. 

Nitrosamine formation is not the only conceivable fragmentation mechanism for compounds of structure I. By analogy to the nitrosative dealkylation reactions discussed above, one might predict that such compounds could also undergo cis elimination of nitroxyl in amide-forming reactions. Such a transformation has possibly been observed (14). During an attempt to synthesize the nitrosamino aldehyde VIII from immonium ion IX, Hecht coworkers were able to isolate only 5-10% of the desired product. The major product proved to be N-methyl-2-pyrrolidone, as shown in Fig. 10. We interpret this as evidence that an intermediate such as li can fragment not only by the Fig. 1... 

The positiveNO ion occurs in compounds like nitroxyl perchlorate, N0 C10, but there is a negative NO ion in nitrites. This negative ion, NO , can be given a structure with only octets, as well, e.g. 

Breakup as indicated by the arrows on this structure would give Fe(III)-OH, citrulline, and 0=N-H, nitroxyl. This is one electron (e + H+) more reduced than NO. Perhaps the adduct forms from Fe(ffl)-0-0. On the other hand, there is evidence that NO synthases may produce nitroxyl or nitroxyl ion NO- as the initial product.537-538 NO and other products such as NzO and N02 may arise rapidly in subsequent reactions. Nitrite is a major oxidation product of NO in tissues.5383 The chemistry of NO in biological systems is complex and not yet fully understood. See also pp. 1754,1755. 

Scheme 10.11 shows a PRE-mediated 5-exo-trig radical cyclisation in which the controlled thermal formation of active radicals from the dormant alkoxyamine 2 is facilitated by steric compression of the alkoxyamine C—O bond by the bulky N-alkyl and O-alkyl groups [8]. Intramolecular H-bonding between a —CH2—OH and the nitroxyl oxygen of the incipient nitroxide in a six-membered cyclic transition structure further facilitated the dissociation of 2. After cyclisation, the resultant primary cyclopentylmethyl radical was trapped by the free nitroxide to form the new dormant isomerised alkoxyamine 3, which is more stable than 2 since the O-alkyl is now primary. The same reaction using TEMPO as the nitroxide component did not work presumably because the C—O bond in the alkoxyamine precursor is much stronger. 

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