Direct Observation of Gas-Phase Hydroxymethylene: Photoionization and Kinetics Resulting from Methanol Photodissociation.

Carbene species play an integral role in high-energy chemistry, transition-metal-carbene chemistry, catalysis, photolytic formation of carbohydrates, and possibly even the formation of interstellar sugars. In 1921, "reactive formaldehyde"─now known as hydroxymethylene (HCOH)─was first implicated as an intermediate in photocatalytic processes. However, due to its transient nature, direct observation of HCOH has predominantly been attained using cryogenic isolation methods. As a result, HCOH gas-phase reactivity measurements have been limited. We directly observed HCOH using photoionization spectroscopy following UV photodissociation of methanol. Our measurements show it reacts slowly with O 2 at room temperature. This work provides evidence for the formation mechanism of HCOH from CH 3 OH and its subsequent reactivity under gas-phase reaction conditions.