C−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylene
| العنوان: | C−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylene |
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| المؤلفون: | Robert Witte, Merle Arrowsmith, Anna Lamprecht, Fabian Schorr, Ivo Krummenacher, Holger Braunschweig |
| المصدر: | Chemistry – A European Journal. 29 |
| بيانات النشر: | Wiley, 2023. |
| سنة النشر: | 2023 |
| مصطلحات موضوعية: | ddc:540, Organic Chemistry, General Chemistry, Catalysis |
| الوصف: | A cyclic alkyl(amino)carbene (CAAC)‐stabilized dicoordinate aminoborylene is synthesized by the twofold reduction of a [(CAAC)BCl\(_{2}\)(TMP)] (TMP=2,6‐tetramethylpiperidyl) precursor. NMR‐spectroscopic, X‐ray crystallographic and computational analyses confirm the cumulenic nature of the central C=B=N moiety. Irradiation of [(CAAC)B(TMP)] (2) resulted in an intramolecular C−C bond activation, leading to a doubly‐fused C\(_{10}\)BN heterocycle, while the reaction with acetonitrile resulted in an aryl migration from the CAAC to the acetonitrile nitrogen atom, concomitant with tautomerization of the latter to a boron‐bound allylamino ligand. One‐electron oxidation of 2 with CuX (X=Cl, Br) afforded the corresponding amino(halo)boryl radicals, which were characterized by EPR spectroscopy and DFT calculations. Placing 2 under an atmosphere of CO afforded the tricoordinate (CAAC,CO)‐stabilized aminoborylene. Finally, the twofold oxidation of 2 with chalcogens led, in the case of N\(_{2}\)O and sulfur, to the splitting of the B−C\(_{CAAC}\) bond and formation of the 2,4‐diamino‐1,3,2,4‐dichalcogenadiboretanes and CAAC‐chalcogen adducts, whereas with selenium a monomeric boraselenone was isolated, which showed some degree of B−Se multiple bonding. |
| وصف الملف: | application/pdf |
| تدمد: | 1521-3765 0947-6539 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::62db847893f027c4aeabd8b3b08b3ca0 https://doi.org/10.1002/chem.202203663 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....62db847893f027c4aeabd8b3b08b3ca0 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15213765 09476539 |
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