Electron-Rich Monovalent Boron: A Platform for Metal Mimicry
Final Report Abstract
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.
Publications
- 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
(See online at https://doi.org/10.1002/anie.201703324) - 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
(See online at https://doi.org/10.1002/anie.201708729) - 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
(See online at https://doi.org/10.1021/jacs.8b07829) - 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
(See online at https://doi.org/10.1126/science.aaq1684) - 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
(See online at https://doi.org/10.1002/chem.201800593) - 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
(See online at https://doi.org/10.1002/anie.201911108) - Metallomimetic Chemistry of Boron, Chem. Rev. 2019, 119, 8231–8261
M.-A. Légaré, C. Pranckevicius, H. Braunschweig
(See online at https://doi.org/10.1021/acs.chemrev.8b00561) - Recent Advances in Boron-Centered Ligands and Their Transition Metal Complexes, Coord. Chem. Rev. 2019, 184–200
J. T. Goettel, H. Braunschweig
(See online at https://doi.org/10.1016/j.ccr.2018.09.013) - 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
(See online at https://doi.org/10.1039/c9sc00657e) - 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
(See online at https://doi.org/10.1126/science.aav9593)
