How Metal Ion Lewis Acidity and Steric Properties Influence the Barrier to Dioxygen Binding, Peroxo O–O Bond Cleavage, and Reactivity
- Award ID(s):
- 1664682
- PAR ID:
- 10206938
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 141
- Issue:
- 38
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 15046 to 15057
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The tetrel bond (TB) between 1,2-benzisothiazol-3-one-2-TF3-1,1-dioxide (T = C, Si) and the O atom of pyridine-1-oxide (PO) and its derivatives (PO-X, X = H, NO2, CN, F, CH3, OH, OCH3, NH2, and Li) is examined by quantum chemical means. The Si∙∙∙O TB is quite strong, with interaction energies approaching a maximum of nearly 70 kcal/mol, while the C∙∙∙O TB is an order of magnitude weaker, with interaction energies between 2.0 and 2.6 kcal/mol. An electron-withdrawing substituent on the Lewis base weakens this TB, while an electron-donating group has the opposite effect. The SiF3 group transfers roughly halfway between the N of the acid and the O of the base without the aid of cooperative effects from a third entity.more » « less
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