Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases
|Corresponding Author||Su，Yuanting; Kong，Lingbing|
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  supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF) and hydride ion affinity (HIA>B(CF)), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of  are further showcased by its ability to abstract hydride and fluoride from EtSiH and AgSbF respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two-electron reduction of  affords stable boron radical cation ⋅ 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. pK (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.
NI Journal Papers
National Natural Science Foundation of China;National Natural Science Foundation of China;Taishan Scholar Foundation of Shandong Province[tsqn202211007];Natural Science Foundation of Shandong Province[ZR2019ZD46];
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Cited Times [WOS]:0
|Document Type||Journal Article|
|Department||Department of Chemistry|
1.School of Chemistry and Chemical Engineering,Shandong University,Jinan,250100,China
2.College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,215123,China
3.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
4.State Key Laboratory of Elemento-Organic Chemistry,Nankai University,Tianjin,300071,China
Lv，Weiwei,Dai，Yuyang,Guo，Rui,et al. Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases[J]. Angewandte Chemie - International Edition,2023,62(36).
Lv，Weiwei.,Dai，Yuyang.,Guo，Rui.,Su，Yuanting.,Ruiz，David A..,...&Kong，Lingbing.(2023).Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases.Angewandte Chemie - International Edition,62(36).
Lv，Weiwei,et al."Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases".Angewandte Chemie - International Edition 62.36(2023).
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