How does Lewis acid affect the reactivity of mononuclear high‐valent chromium–oxo species? A theoretical study. (15th September 2021)

• Record Type: Journal Article
• Authors: Choi, Yunhee; Pandey, Bhawana; Li, Xiao‐Xi; Lee, Yong‐Min; Cho, Kyung‐Bin; Nam, Wonwoo
• Is Part Of: Bulletin of the Korean Chemical Society. Volume 42:Number 11(2021)
• Page Start: 1501
• Page End: 1505
• Publication Date: 2021-09-15
• Subjects: DFT CH bond activation -- high‐valent chromium–oxo -- Lewis acid -- sulfoxidation; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/bkcs.12397
• Languages: English
• ISSNs: 0253-2964

Abstract

Abstract: Density functional theory calculations were performed to study the Lewis acid (Sc 3+ ) effects on the reactivity of ultrahigh‐valent chromium‐oxo species toward both CH bond activation and sulfoxidation reactions. Calculations confirm that the oxidizing power of chromium‐oxo species is enhanced by binding Sc 3+ ion. In sulfoxidation reactions, especially, binding Sc 3+ ion enhances the redox potential of the chromium‐oxo species, whereby the activation barrier is decreased dramatically. The details of the reactions obtained by theory are disclosed in this work. Abstract : A series of theoretical studies have been carried out to illustrate the influence of Lewis acid on high‐valent chromium–oxo species. The binding of Lewis acid can enhance the oxidizing power of the chromium–oxo species. In sulfoxidation reactions, this occurs through an increase of the redox potential of Cr V O TAML cation radical upon binding Lewis acid to the carbonyl (C═O) oxygen atom of the tetraamido macrocyclic ligand.