CHNO - Formylnitrene, Cyanic, Isocyanic, Fulminic, and Isofulminic Acids and their Interrelationships at DFT and CASPT2 Levels of Theory.

Abstract

Fulminic and cyanic acids played a decisive role in the conception of isomerism 200 years ago. Cyanic (HOCN), isocyanic (HNCO), and fulminic (HCNO) acids have been detected in several interstellar sources, but isofulminic acid (HONC) is little known. Here we examine the interrelationships between the four acids and formylnitrene, HC(O)N, at the CASPT2 and three DFT levels. Formylnitrene has a triplet ground state, T0, a closed shell singlet (CSS), S0, and an open-shell singlet (OSS), S1, lying ∼7 and 27 kcal/mol above T0, respectively. The CSS is weakly stabilized by a 12 kcal/mol bond between the N and the O atoms. A conical intersection 12 kcal/mol above T0 permits easy T0-S0 interchange. Formyl azide and formylnitrene (T0 and S0) are isomerized thermally to HNCO. HOCN is best obtained via dissociation of the nitrene (or of HNCO) to H• + NCO• radicals ∼46 kcal/mol above the T0 nitrene. Isofulminic acid, HONC, isomerizes readily to cyanic acid, HOCN, in thermal and photochemical reactions. Fulminic acid, HCNO, can isomerize to HNCO via CSS formylnitrene. Easy tautomerization prevents the preparation of HOCN in quantity. The barrier to isomerization is strongly reduced in small hydrogen-bonded aggregates so that trace amounts of HOCN can exist in equilibrium with HNCO.