The menagerie of aromatic carbenes

Carbenes are commonly generated by irradiation or pyrolysis of an appropriate diazo-compound (2). Apart from differences readily traced to the change in temperature, the chemical properties of the carbenes formed from photolysis and from thermolysis are usually quite similar. These observations 

The diazo-compounds and corresponding aromatic carbenes that form the basis for our dissection of structure and reactivity are shown in Table 1. The carbenes in this group are carefully chosen so that the variation in structure is systematic the theory identifies the carbene bond angle and certain electronic factors as controlling chemical and physical properties, and as far as possible, these two features are varied independently of each other for these carbenes. Table 2 lists some other aromatic carbenes that have been studied. In general, the structures of these carbenes are not simply related to each other. Nevertheless, the principles uncovered by analysis of the compounds of Table 1 can be readily extended to those of Table 2. 

Of course the structural changes represented in Table 1 are much more complex than the simple bond angle plus electronic effect analysis reveals. For example, solvation of the carbene may depend on the details of its structure, and solvation undoubtedly influences chemical and physical properties (Langan et al., 1984). Nonetheless, it is possible to develop a good grasp of the most important properties of aromatic carbenes from the simple considerations described above. Before we proceed to examine these relationships in more detail, the carbene properties of interest must be identified, and the experimental procedures available for measurement of these properties must be critically considered. 

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