C−C and C−N Bond Activation, Lewis‐Base Coordination and One‐ and Two‐Electron Oxidation at a Linear Aminoborylene
Zitieren Sie bitte immer diese URN: urn:nbn:de:bvb:20-opus-312491
- 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 acetonitrileA 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.…
Autor(en): | Robert Witte, Merle Arrowsmith, Anna Lamprecht, Fabian Schorr, Ivo Krummenacher, Holger BraunschweigORCiD |
---|---|
URN: | urn:nbn:de:bvb:20-opus-312491 |
Dokumentart: | Artikel / Aufsatz in einer Zeitschrift |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Chemistry – A European Journal |
Erscheinungsjahr: | 2023 |
Band / Jahrgang: | 29 |
Heft / Ausgabe: | 16 |
Aufsatznummer: | e202203663 |
Originalveröffentlichung / Quelle: | Chemistry – A European Journal 2023, 29(16):e202203663. DOI: 10.1002/chem.202203663 |
DOI: | https://doi.org/10.1002/chem.202203663 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Freie Schlagwort(e): | bond activation; boraselenone; dicoordinate borylene; one-electron oxidation; push-pull stabilization |
Datum der Freischaltung: | 21.06.2023 |
Lizenz (Deutsch): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |