Synthesis of methanediol [CH 2 (OH) 2 ]: The simplest geminal diol

Significance Methanediol [CH 2 (OH) 2 ] represents a pivotal atmospheric volatile organic compound and plays a fundamental role in aerosol growth. Although sought for decades, methanediol has never been identified due to the inherent dehydration tendency of two adjacent hydroxyl groups (OH) at the same carbon atom. Here, we prepare and identify methanediol via processing of low-temperature ices followed by sublimation into the gas phase. These findings open up a concept to synthesize and characterize unstable geminal diols—critical organic transients in Earth’s atmosphere. The excited state dynamics of oxygen may also lead to methanediol in methanol-rich interstellar ices in cold molecular clouds, followed by sublimation in star-forming regions and prospective detection of these reactive intermediates in the gas phase by radiotelescopes.