Nucleophilic addition and substitution at coordinatively saturated boron by facile 1,2-hydrogen shuttling onto a carbene donor
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- The reaction of [(cAAC\(^{Me}\))BH\(_{3}\)] (cAAC\(^{Me}\) = 1-(2,6-iPr\(_{2}\)C\(_{6}\)H\(_{3}\))-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li\(^{+}\)[(cAAC\(^{Me}\)H)BH\(_{2}\)R]− (R = sp\(^{3}\)-, sp\(^{2}\)-, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me3SiCl or spontaneous LiHThe reaction of [(cAAC\(^{Me}\))BH\(_{3}\)] (cAAC\(^{Me}\) = 1-(2,6-iPr\(_{2}\)C\(_{6}\)H\(_{3}\))-3,3,5,5-tetramethylpyrrolidin-2-ylidene) with a range of organolithium compounds led to the exclusive formation of the corresponding (dihydro)organoborates, Li\(^{+}\)[(cAAC\(^{Me}\)H)BH\(_{2}\)R]− (R = sp\(^{3}\)-, sp\(^{2}\)-, or sp-hybridised organic substituent), by migration of one boron-bound hydrogen atom to the adjacent carbene carbon of the cAAC ligand. A subsequent deprotonation/salt metathesis reaction with Me3SiCl or spontaneous LiH elimination yielded the neutral cAAC-supported mono(organo)boranes, [(cAAC\(^{Me}\)H)BH\(_{2}\)R]− (R]. Similarly the reaction of [cAAC\(^{Me}\))BH\(_{3}\)] with a neutral donor base L resulted in adduct formation by shuttling one boron-bound hydrogen to the cAAC ligand, to generate [(cAAC\(^{Me}\)H)BH\(_{2}\)L], either irreversibly (L = cAAC\(^{Me}\)) or reversibly (L = pyridine). Variable-temperature NMR data and DFT calculations on [(cAAC\(^{Me}\)H)BH\(_{2}\)(cAAC\(^{Me}\))] show that the hydrogen on the former carbene carbon atom exchanges rapidly with the boron-bound hydrides.…
Autor(en): | Dominic AuerhammerORCiD, Merle ArrowsmithORCiD, Holger BraunschweigORCiD, Rian D. DewhurstORCiD, J. Oscar C. Jiménez-HallaORCiD, Thomas Kupfer |
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URN: | urn:nbn:de:bvb:20-opus-170255 |
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): | Chemical Science |
Erscheinungsjahr: | 2017 |
Band / Jahrgang: | 8 |
Heft / Ausgabe: | 10 |
Seitenangabe: | 7066–7071 |
Originalveröffentlichung / Quelle: | Chemical Science, 2017, 8(10), 7066-7071. DOI: 10.1039/c7sc03193a |
DOI: | https://doi.org/10.1039/c7sc03193a |
PubMed-ID: | https://pubmed.ncbi.nlm.nih.gov/29147534 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Freie Schlagwort(e): | boron-bound hydrogen; carbene donor; nucleophilic addition; nucleophilic substitution |
Datum der Freischaltung: | 23.09.2019 |
Lizenz (Deutsch): | CC BY: Creative-Commons-Lizenz: Namensnennung |