Combined Computational and Experimental Study on Nitrilimines Generated from 2,5-Substituted Tetrazoles

Abstract

Nitrilimines are a useful chemical intermediate for the synthesis of a variety of nitrogen heterocycles for use in pharmaceuticals, energetics, and other energy storage applications. The limitations of this intermediate are explored here with a paired experimental and computational study into the viable substituents for its generation from 2,5-substituted tetrazoles. Nitrilimines generated via the loss of nitrogen gas from these tetrazoles are possible with almost any substitution at the 5-position, with electron withdrawing groups aiding in formation. The lack of an aryl or heteroaryl substituent at the 2-position of the tetrazole prevented nitrilimine formation in all experiments, an observation that was supported by computation.