Conformer-specific [1,2]-tunnelling in captodatively-stabilized cyanohydroxycarbene (NC-C[combining umlaut]-OH).

We report the gas-phase preparation of cyanohydroxycarbene by high-vacuum flash pyrolysis of ethyl 2-cyano-2-oxoacetate and subsequent trapping of the pyrolysate in an inert argon matrix at 3 K. After irradiation of the matrix with green light for a few seconds singlet -cyanohydroxycarbene rearranges to its -conformer. Prolonged irradiation leads to the formation of cyanoformaldehyde and isomeric isocyanoformaldehyde. - and -cyanohydroxycarbene were characterized by matching matrix IR and UV/Vis spectroscopic data with coupled cluster and TD-DFT computations. -cyanohydroxycarbene undergoes a conformer-specific [1,2]-tunnelling reaction through a 33.3 kcal mol barrier (the highest penetrated barrier of all H-tunnelling reactions observed to date) to cyanoformaldehyde with a half-life of 23.5 ± 0.5 d; this is the longest half-life reported for an H-tunnelling process to date. During the tunnelling reaction the -conformer remains unchanged over the same period of time and the Curtin-Hammett principle does not apply. NIR irradiation of the O-H stretching overtone does not enhance the tunnelling rate vibrational activation. Push-pull stabilisation of hydroxycarbenes through σ- and π-withdrawing groups therefore is even more stabilizing than push-push substitution.