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Title: 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
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ;
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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  1. 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. 
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