Back to Search
Start Over
Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases.
- Source :
- Angewandte Chemie International Edition; Sep2023, Vol. 62 Issue 36, p1-8, 8p
- Publication Year :
- 2023
-
Abstract
- This report unveils an advancement in the formation of a Lewis superacid (LSA) and an organic superbase by the geometrical deformation of an organoboron species towards a T‐shaped geometry. The boron dication [2]2+ supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF5) and hydride ion affinity (HIA>B(C6F5)3), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of [2]2+ are further showcased by its ability to abstract hydride and fluoride from Et3SiH and AgSbF6 respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two‐electron reduction of [2]2+ affords stable boron radical cation [2]⋅+ and borylene 2, respectively. The former species has an extremely high spin density of 0.798e at the boron atom, whereas the latter compound has been demonstrated to be a strong organic base (calcd. pKBH+ (MeCN)=47.4) by both theoretical and experimental assessment. Overall, these results demonstrate the strong ability of geometric constraining to empower the central boron atom. [ABSTRACT FROM AUTHOR]
- Subjects :
- SUPERACIDS
RADICAL cations
ORGANIC bases
CARBONYL compounds
SPECIES
Subjects
Details
- Language :
- English
- ISSN :
- 14337851
- Volume :
- 62
- Issue :
- 36
- Database :
- Complementary Index
- Journal :
- Angewandte Chemie International Edition
- Publication Type :
- Academic Journal
- Accession number :
- 171105799
- Full Text :
- https://doi.org/10.1002/anie.202308467