Novel reactions of cyclocarbaphosphazenes and cyclocarbathiazenes

The hybrid inorganic-organic heterocycles, pentachlorocyclocarba phosphazen e, (ClCN)(2)(Cl2PN) and triachlorocyclocarbathiazene. (ClCN)(2)(ClSN) were synthesized and their reaction chemistry explored with emphasis on dealkyla tion reactions of the heterocycles with tertiary amines. Reactions of (ClCN )(2)(Cl2PN) were carried out with bicyclic, unsymmetric and sterically hind ered tertiary amines as well as aminomethyl ferrocenes. In all cases, the C -Cl bonds of the carbaphosphazene were found to react with the tertiary ami nes resulting in the cleavage of an alkyl group and regiospecific substitut ion of the dialkylamino group on the ring carbon atoms of the heterocycle. While bicyclic amines were found to undergo ring opening, the preference of the cleaved group in the case of unsymmetrical amines were found to depend on the stability of the carbocations formed. Similar dealkylation was obse rved in the reactions of the carbathiazene (ClCN)(2)(ClCN) with tertiary am ines.