We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
C versus O Protonation in Zincate Anions: A Simple Gas‐Phase Model for the Surprising Kinetic Stability of Organometallics.
- Authors
Rahrt, Rene; Koszinowski, Konrad
- Abstract
For better understanding the intrinsic reactivity of organozinc reagents, we have examined the protolysis of the isolated zincate ions Et3Zn−, Et2Zn(OH)−, and Et2Zn(OH)2Li− by 2,2,2‐trifluoroethanol in the gas phase. The protonation of the hydroxy groups and the release of water proceed much more efficiently than the protonation of the ethyl groups and the liberation of ethane. Quantum‐chemical computations and statistical‐rate theory calculations fully reproduce the experimental findings and attribute the lower reactivity of the more basic ethyl moiety to higher intrinsic barriers, which override the thermodynamic preference for its protonation. Thus, our minimalistic gas‐phase model provides evidence for the intrinsically low reactivity of organozinc reagents toward proton donors and helps to explain their remarkable kinetic stability against moisture and even protic media.
- Subjects
ANIONS; ETHYL group; ION-molecule collisions; PROTON transfer reactions
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 22, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202203611