Elektronenreiches, monovalentes Bor: eine Plattform für metallähnliche Reaktivitäten

• Antragsteller: Professor Dr. Holger Braunschweig
• Fachliche Zuordnung: Anorganische Molekülchemie - Synthese, Charakterisierung
• Förderung: Förderung von 2017 bis 2020
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 325229020

• Erstellungsjahr: 2020

Zusammenfassung der Projektergebnisse

This project has opened up huge opportunities for future research in our group. The TM-borylene chemistry, upon which the original proposal was based, has seen a large expansion of promising TM-borylene reagents, as well as a number of new modes of liberation of the borylene ligand using Lewis bases and other reagents such as chalcogens, leading to new (metal-free) monovalent boron compounds, iminoboranes as well as a number of new classes of boron-containing heterocycles. The metal-free chemistry of monovalent boron compounds, a more recent offshoot of this chemistry, has already witnessed some major breakthroughs such as the first fixation, reduction and dimerization of N2 at a main-group atom, and ultimately the confirmed one-pot synthesis of ammonium from N2 using this system. A huge number of possibilities beckon from these results in different directions, namely: (a) the use of monovalent boron species in the activation of other challenging small molecules, and (b) the development of the N2 fixation chemistry towards practical methods to prepare ammonia and other value-added nitrogencontaining compounds.

Projektbezogene Publikationen (Auswahl)

• Synthesis and Trapping of Iminoboranes via M=B/C=N Bond Metathesis, Angew. Chem. Int. Ed. 2017, 56, 7975–7979
  B. Borthakur, H. Braunschweig, A. Deißenberger, T. Dellermann, R. D. Dewhurst, I. Krummenacher, M. Nutz, A. K. Phukan, M. Schäfer
  
• The First Boron-Tellurium Double Bond: Direct Insertion of Heavy Chalcogens into a Mn=B Double Bond, Angew. Chem. Int. Ed. 2017, 56, 15760–15763
  S. Liu, M.-A. Légaré, D. Auerhammer, A. Hofmann, H. Braunschweig
  
• A Boradiselenirane and a Boraditellurirane: Isolable Heavy Analogs of Dioxiranes and Dithiiranes, J. Am. Chem. Soc. 2018, 140, 11223–11226
  S. Liu, M.-A. Légaré, A. Hofmann, H. Braunschweig
  
• Nitrogen fixation and reduction at boron, Science 2018, 359, 896–900
  M.-A. Légaré, G. Bélanger-Chabot, R. D. Dewhurst, E. Welz, I. Krummenacher, B. Engels, H. Braunschweig
  
• Release of Isonitrile- and NHC-stabilized Borylenes from Group VI Terminal Borylene Complexes, Chem. Eur. J. 2018, 24, 6843–6847
  M. Nutz, B. Borthakur, C. Pranckevicius, R. D. Dewhurst, M. Schäfer, T. Dellermann, F. Glaab, M. Thaler, A. K. Phukan, H. Braunschweig
  
• Boron: Its role in energy related research and applications, Angew. Chem. Int. Ed.
  Z. Huang, S. Wang, R. D. Dewhurst, N. V. Ignat'ev, M. Finze, H. Braunschweig
  
• Metallomimetic Chemistry of Boron, Chem. Rev. 2019, 119, 8231–8261
  M.-A. Légaré, C. Pranckevicius, H. Braunschweig
  
• Recent Advances in Boron-Centered Ligands and Their Transition Metal Complexes, Coord. Chem. Rev. 2019, 184–200
  J. T. Goettel, H. Braunschweig
  
• Synthesis of unsymmetrical B2E2 and B2E3 heterocycles by borylene insertion into boradichalcogeniranes, Chem. Sci. 2019, 10, 4662–4666
  S. Liu, M.-A. Légaré, A. Hofmann, A. Rempel, S. Hagspiel, H. Braunschweig
  
• The reductive coupling of dinitrogen, Science 2019, 363, 1329–1332
  M.-A. Légaré, M. Rang, G. Bélanger-Chabot, J. I. Schweizer, I. Krummenacher, R. Bertermann, M. Arrowsmith, M. C. Holthausen, H. Braunschweig