Cooperative Bond Activation and Catalytic CO2 Functionalization with a Geometrically Constrained Bis(silylene)-Stabilized Borylene
Metal-ligand cooperativity has emerged as an important strategy to tune the reactivity of transition-metal complexes for the catalysis and activation of small molecules. Studies of main-group compounds, however, are scarce. Here, we report the synthesis, structural characterization, and reactivity of a geometrically constrained bis(silylene)-stabilized borylene. The one-pot reaction of [(SiNSi)Li(OEt2)] (SiNSi = 4,5-bis(silylene)-2,7,9,9-tetramethyl-9H-acridin-10-ide) with 1 equiv of [BBr3(SMe2)] in toluene at room temperature followed by reduction with 2 equiv of potassium graphite (KC8) leads to borylene [(SiNSi)B] (1), isolated as blue crystals in 45% yield. X-ray crystallography shows that borylene (1) has a tricoordinate boron center with a distorted T-shaped geometry. Computational studies reveal that the HOMO of 1 represents the lone pair orbital on the boron center and is delocalized over the Si-B-Si unit, while the geometric perturbation significantly increases its energy. Borylene (1) shows single electron transfer reactivity toward tris(pentafluorophenyl)borane (B(C6F5)3), forming a frustrated radical pair [(SiNSi)B]•+[B(C6F5)3]•-, which can be trapped by its reaction with PhSSPh, affording an ion pair [(SiNSi)BSPh][PhSB(C6F5)3] (3). Remarkably, the cooperation between borylene and silylene allows the facile cleavage of the N-H bond of aniline, the P-P bond in white phosphorus, and the C═O bond in ketones and carbon dioxide, thus representing a new type of main-group element-ligand cooperativity for the activation of small molecules. In addition, 1 is a strikingly effective catalyst for carbon dioxide reduction. Computational studies reveal that the cooperation between borylene and silylene plays a key role in the catalytic chemical bond activation process.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:145 |
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| Enthalten in: |
Journal of the American Chemical Society - 145(2023), 12 vom: 29. März, Seite 7011-7020 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Chen, Xi [VerfasserIn] |
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| Anmerkungen: |
Date Completed 29.03.2023 Date Revised 29.03.2023 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.3c00949 |
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| funding: |
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NLM35444686X |
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| 245 | 1 | 0 | |a Cooperative Bond Activation and Catalytic CO2 Functionalization with a Geometrically Constrained Bis(silylene)-Stabilized Borylene |
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| 500 | |a Date Revised 29.03.2023 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Metal-ligand cooperativity has emerged as an important strategy to tune the reactivity of transition-metal complexes for the catalysis and activation of small molecules. Studies of main-group compounds, however, are scarce. Here, we report the synthesis, structural characterization, and reactivity of a geometrically constrained bis(silylene)-stabilized borylene. The one-pot reaction of [(SiNSi)Li(OEt2)] (SiNSi = 4,5-bis(silylene)-2,7,9,9-tetramethyl-9H-acridin-10-ide) with 1 equiv of [BBr3(SMe2)] in toluene at room temperature followed by reduction with 2 equiv of potassium graphite (KC8) leads to borylene [(SiNSi)B] (1), isolated as blue crystals in 45% yield. X-ray crystallography shows that borylene (1) has a tricoordinate boron center with a distorted T-shaped geometry. Computational studies reveal that the HOMO of 1 represents the lone pair orbital on the boron center and is delocalized over the Si-B-Si unit, while the geometric perturbation significantly increases its energy. Borylene (1) shows single electron transfer reactivity toward tris(pentafluorophenyl)borane (B(C6F5)3), forming a frustrated radical pair [(SiNSi)B]•+[B(C6F5)3]•-, which can be trapped by its reaction with PhSSPh, affording an ion pair [(SiNSi)BSPh][PhSB(C6F5)3] (3). Remarkably, the cooperation between borylene and silylene allows the facile cleavage of the N-H bond of aniline, the P-P bond in white phosphorus, and the C═O bond in ketones and carbon dioxide, thus representing a new type of main-group element-ligand cooperativity for the activation of small molecules. In addition, 1 is a strikingly effective catalyst for carbon dioxide reduction. Computational studies reveal that the cooperation between borylene and silylene plays a key role in the catalytic chemical bond activation process | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Yang, Yin |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Hao |e verfasserin |4 aut | |
| 700 | 1 | |a Mo, Zhenbo |e verfasserin |4 aut | |
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