A study of the thermal decomposition of azidoacetone by photoelectron and matrix isolation spectroscopy

2-Azidoacetone (N3CH2COCH3) has been synthesized and characterized by a var iety of spectroscopic techniques, and the thermal decomposition of this mol ecule at temperatures in the region 300-1150 K has been studied by matrix i solation infrared spectroscopy and real-time ultraviolet photoelectron spec troscopy. The results show the effectively simultaneous production of six p rominent decomposition products: CH2NH, CH2CO, HCN, CO, N-2, and CH3CHO, an d several reaction pathways are proposed to account for their formation. Re sults of ab initio molecular orbital calculations indicate that the primary reaction intermediate is the imine HNCHCOCH3, with the nitrene NCH2COCH3 b eing a transition state. No experimental evidence was found for the presenc e of the imine HNCHCOCH3, but mechanistic considerations, and the existence of several weak unassigned IR bands point to the presence of a further dec omposition product, which may be CH2NCH3.