Abstract
Experiment shows that there is no carbon kinetic isotope effect in the formation of CHsMgl from CH3I (k12/k13 = 0.9992, σ = 0.0005). Calculations indicate that an observable isotope effect should accompany this reaction if it proceeds by an inner-sphere electron-transfer mechanism in which breakage of the carbon-halogen bond must be involved in the rate-determining step. Accordingly, it is proposed that the alternative mechanism must be followed, with the rate-determining step involving formation of a radical-ion pair by outer-sphere electron transfer from the magnesium to the organic halide.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 3163-3166 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 100 |
| Issue number | 10 |
| DOIs | |
| State | Published - Jan 1 1978 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
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Mechanism of Formation of Grignard Reagents. / Vogler, Erwin A.; Stein, R. L.; Hayes, J. M.
In: Journal of the American Chemical Society, Vol. 100, No. 10, 01.01.1978, p. 3163-3166.Research output: Contribution to journal › Article
TY - JOUR
T1 - Mechanism of Formation of Grignard Reagents
AU - Vogler, Erwin A.
AU - Stein, R. L.
AU - Hayes, J. M.
PY - 1978/1/1
Y1 - 1978/1/1
N2 - Experiment shows that there is no carbon kinetic isotope effect in the formation of CHsMgl from CH3I (k12/k13 = 0.9992, σ = 0.0005). Calculations indicate that an observable isotope effect should accompany this reaction if it proceeds by an inner-sphere electron-transfer mechanism in which breakage of the carbon-halogen bond must be involved in the rate-determining step. Accordingly, it is proposed that the alternative mechanism must be followed, with the rate-determining step involving formation of a radical-ion pair by outer-sphere electron transfer from the magnesium to the organic halide.
AB - Experiment shows that there is no carbon kinetic isotope effect in the formation of CHsMgl from CH3I (k12/k13 = 0.9992, σ = 0.0005). Calculations indicate that an observable isotope effect should accompany this reaction if it proceeds by an inner-sphere electron-transfer mechanism in which breakage of the carbon-halogen bond must be involved in the rate-determining step. Accordingly, it is proposed that the alternative mechanism must be followed, with the rate-determining step involving formation of a radical-ion pair by outer-sphere electron transfer from the magnesium to the organic halide.
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UR - http://www.scopus.com/inward/citedby.url?scp=0011087919&partnerID=8YFLogxK
U2 - 10.1021/ja00478a034
DO - 10.1021/ja00478a034
M3 - Article
VL - 100
SP - 3163
EP - 3166
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 10
ER -