Gas‐Phase Structure Determination of Dihydroxycarbene,One of the Smallest Stable Singlet Carbenes |
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| Authors: | Dr Caroline C Womack Dr Kyle N Crabtree Laura McCaslin Dr Oscar Martinez Jr Prof Robert W Field Prof John F Stanton Dr Michael C McCarthy |
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| Institution: | 1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA);2. Harvard‐Smithsonian Center for Astrophysics, Cambridge, MA 02138 (USA);3. Department of Chemistry & Biochemistry, University of Texas at Austin, Austin, TX 78712 (USA) |
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| Abstract: | Carbenes are reactive molecules of the form R1? C?? R2 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? C?? 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? C?? OH contains two very short CO single bonds (ca. 1.32 Å). Detection of HO? C?? OH in the gas phase firmly establishes that it is stable to isomerization, yet it has been underrepresented in discussions of the CH2O2 chemical system and its atmospherically relevant isomers: formic acid and the Criegee intermediate CH2OO. |
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| Keywords: | atmospheric chemistry carbenes microwave spectroscopy reactive intermediates structure elucidation |
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