Reactive Intermediates and Unusual Molecules: 70 Years with Fascinating Chemistry

This account details the author's work with reactive intermediates and unusual molecules, starting with amateur rocket propellants like zinc dust and sulfur followed by experiments with highly sensitive compounds, nitrogen trichloride, and fulminating gold. Research on alkyl and aryl cyanates, ROCN, the inorganic and organic fulminates, XCNO, and the CHNO and CRNO isomers lead to detailed chemical and spectroscopic (IR, UV, ESR, MS, MW, and PES) investigations of reactive intermediates generated by flash vacuum pyrolysis, matrix isolation, and matrix photolysis, in particular nitrenes and carbenes from azides, diazo compounds, triazoles, tetrazoles, and sydnones, as well as nitrile imines, ylides, and oxides, imidoylnitrenes, carbodiimides, cyanocyclopentadiene, fulvenallene, numerous ketenes, propadienones, iminopropadienones, sulfur compounds like SCCS, N₂S, and RCNS, the HCN dimers CH₂NCN and HNCHCN, and numerous other compounds. Along the way, equipment for flash vacuum pyrolysis in conjunction with IR, UV, and ESR spectroscopies and mass spectrometry was developed.