Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes
Author(s)Crabtree, Kyle N.; McCaslin, Laura; Martinez, Oscar; Stanton, John F.; McCarthy, Michael C.; Womack, Caroline C.; Field, Robert W; ... Show more Show less
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Carbenes are reactive molecules of the form R[superscript 1]-C̈-R[superscript 2] that play a role in topics ranging from organic synthesis to gas‐phase oxidation chemistry. We report the first experimental structure determination of dihydroxycarbene (HO-C̈-OH), one of the smallest stable singlet carbenes, using a combination of microwave rotational spectroscopy and high‐level coupled‐cluster calculations. The semi‐experimental equilibrium structure derived from five isotopic variants of HO-C̈-OH contains two very short CO single bonds (ca. 1.32 Å). Detection of HO-C̈-OH in the gas phase firmly establishes that it is stable to isomerization, yet it has been underrepresented in discussions of the CH[subscript 2]O[subscript 2] chemical system and its atmospherically relevant isomers: formic acid and the Criegee intermediate CH[superscript 2]OO. Keywords: atmospheric chemistry, carbenes, microwave spectroscopy, reactive intermediates, structure elucidation
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Angewandte Chemie International Edition
Womack, Caroline C., et al. “Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes.” Angewandte Chemie International Edition, vol. 53, no. 16, Apr. 2014, pp. 4089–92.