March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 7th Edition (2013)
Part I. Introduction
Chapter 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes
5.E. Nitrenes
Nitrenes (R–N),427 are the nitrogen analogues of carbenes, and most of the comments about carbenes also applies to them. Nitrenes are too reactive for isolation under ordinary conditions,428 although ab initio calculations show that nitrenes are more stable than carbenes with an enthalpy difference of 25–26 kcal mol−1 (104.7–108.8 kJ mol−1).429
Alkyl nitrenes have been isolated by trapping in matrices at 4 K,430 while aryl nitrenes, which are less reactive, can be trapped at 77 K.431 The ground state of NH, and probably of most nitrenes,432 is a triplet, although nitrenes can be generated in both triplet433 and singlet states. A quartet ground-state nitreno radical has been reported.434 In additions of EtOOC–N to C=C double bonds two species are involved, one of which adds in a stereospecific manner and the other not. By analogy with Skell's proposal involving carbenes (Sec. 5.D.i) these are taken to be the singlet and triplet species, respectively.435
The two principal means of generating nitrenes are analogous to those used to form carbenes.
1. Elimination. An example is
2. Breakdown of Certain Double-Bond Compounds. The most common method of forming nitrenes is photolytic or thermal decomposition of azides,436
The unsubstituted nitrene (NH) has been generated by photolysis of electric discharge through NH3, N2H4, or HN3.
The reactions of nitrenes are also similar to those of carbenes.437 As in that case, many reactions in which nitrene intermediates are suspected probably do not involve free nitrenes. It is often very difficult to obtain proof in any given case that a free nitrene is or is not an intermediate.
1. Insertion (see Reaction 12-13). Nitrenes, especially acyl nitrenes and sulfonyl nitrenes, can insert into C–H and certain other bonds, for example,
2. Addition to C=C bonds (see Reaction 15-54):
3. Rearrangements.413 Alkyl nitrenes do not generally give either of the two preceding reactions because rearrangement is more rapid, for example,
Such rearrangements are so rapid that it is usually difficult to exclude the possibility that a free nitrene was never present at all; that is, that migration takes place at the same time the nitrene is formed438 (see Reaction 18-12). However, the rearrangement of naphthylnitrenes to novel bond-shift isomers has been reported.439
4. Abstraction, For example,
5. Dimerization. One of the principal reactions of NH is dimerization to diimide (N2H2). Azobenzenes are often obtained in reactions where aryl nitrenes are implicated:440
It would thus seem that dimerization is more important for nitrenes than it is for carbenes, but again it has not been proven that free nitrenes are actually involved.
At least two types of nitrenium ions,441 the nitrogen analogues of carbocations, can exist as intermediates, although much less work has been done in this area than on carbocations. In one type (76), the nitrogen is bonded to two atoms (R or R′ can be H),442 and in the other (77) to only one atom.443 When R = H in 76 the species is a protonated nitrene. Like carbenes and nitrenes, nitrenium ions can exist in singlet or triplet states.444
Notes
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