Phosphorus—nitrogen bonds hydrogen halides

In intramolecular arylations, a new bond is created between two aromatic moieties of the same molecule or between an aromatic nucleus and an atom of a side-chain. Many intramolecular arylation reactions of homocyclic and heterocyclic aromatic halides have been studied mainly in view of their synthetic applications, and it is not always clear which mechanistic pathway is followed. The reaction may start with homolytic or heterolytic dissociation of the carbon-halogen bond and proceed by attack of the aryl radical or aryl cation on another part of the molecule. Electrocyclization followed by elimination of hydrogen halide is another possibility. Especially when heteroatoms such as nitrogen, sulphur or phosphorus are involved, the initial step may be a nucleophilic attack on the carbon atom bearing the halide atom. 

The phosphorus-nitrogen bond is readily cleaved by hydrogen halides (47,107,118, 236, 277, 213, 237). 

A survey of the hydrides, oxides, hydroxides, and halides highlights the network components. The hydrides of nitrogen and phosphorus emphasize the uniqueness of the lightest element. Unlike the polar ammonia, the nonpolar phosphine is a poor base and not capable of forming hydrogen bonds. Arsine is less stable than phosphine, and its decomposition is the basis of the criminological Marsh test for the presence of arsenic. 

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