Nitrogen atomic size

Nitrogen-containing fulvalenes have not been systematically studied by mass spectroscopy. Only isolated data for several examples of compounds have been reported. Most of the data consist of electron impact (El) mass spectra recorded for analytical purposes. Only a minor fraction dealt with the characterization of ion structures or focused on the effects of substituents, the ring size of fulvalenes, or the number and arrangement of nitrogen atoms and the fragmentation pathways. 

Cyclazines are conjugated cyclic molecules in which planarity is secured by three covalent bonds to a central nitrogen atom. They differ in the size of the individual ring units. In the nomenclature of cyclazines, the name is preceded by the number of jt-centers between the points of attachment to the nitrogen which are arranged by increasing number and put in brackets, e.g. [3.3.3]cyclazine (1) and [2.3.4]cyclazine (2). 

The synthetic potential of such transformations for the preparation of medium-size heterocycles172 has been discussed elsewhere2. It is generally accepted that the reaction between thiirene dioxides and enamines is a stepwise (nonconcerted) thermal [2 -I- 2] cycloaddition. However, a concerted [4 + 2] cycloaddition, in which the lone pair of the enamine nitrogen atom participates, cannot be excluded. 

In comparison with the decomposition of taws-azoalkanes 20 a much larger group size effect has been found for the thermolysis rates of a few c/s-azoalkanes 24. Due to the repulsion of the free electron pairs on the two nitrogen atoms and due to steric interaction between the cis oriented alkyl groups cis azoalkanes 24 decom-... 

Reductive cleavage of the N-N bond in bicyclic systems containing a ring junction hydrazine subunit presents a facile route to medium-sized heterocycles containing two or more nitrogen atoms and the subject was duly covered in CHEC-II(1996) <1996CHEC-II(8)747>. No substantial progress has been reported since its publication. 

Note that the N3- ion (radius 171 pm) is much larger than the nitrogen atom, for which the covalent radius is only 71 pm. The oxygen atom (radius 72 pm) is approximately half the size of the oxide ion... 

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