Gas-Phase Structure Determination of Dihydroxycarbene, One of the Smallest Stable Singlet Carbenes
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AngChem_53_p4089.pdf
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Author(s)
Crabtree, Kyle N.
McCaslin, Laura
Martinez, Oscar
Stanton, John F.
McCarthy, Michael C.
Womack, Caroline C.
Field, Robert W
Date Issued
March 2014
Journal
Angewandte Chemie International Edition
Publisher
Wiley Blackwell
Citation
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.
Version
Original manuscript
Abstract
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
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1002/anie.201311082
