Gas-phase carbene radical anions: new mechanistic insights |
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Authors: | Villano Stephanie M Eyet Nicole Lineberger W Carl Bierbaum Veronica M |
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Institution: | JILA, University of Colorado and the National Institute of Standards and Technology and the University of Colorado, Department of Chemistry and Biochemistry, 215 UCB, Boulder, Colorado 80309-0215, USA. |
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Abstract: | The gas-phase reactivity of the CHCl*- anion has been investigated with a series of halomethanes (CCl4, CHCl3, CH2Cl2, and CH3Cl) using a FA-SIFT instrument. Results show that this anion primarily reacts via substitution and by proton transfer. In addition, the reactions of CHCl*- with CHCl3 and CH2Cl2 form minor amounts of Cl2*- and Cl-. The isotopic distribution of these two products is consistent with an insertion-elimination mechanism, where the anion inserts into a C-Cl bond to form an unstable intermediate, which eliminates either Cl2*- or Cl- and Cl*. Neutral and cationic carbenes are known to insert into single bonds; however, this is the first observation of such reactivity for carbene anions. |
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