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  • 2021 (4)
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  • English (4)
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  • boron (3)
  • inorganic chemistry (2)
  • Beryllium (1)
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  • Decarbonylierung (1)
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  • Braunschweig, Holger (5)
  • Gärtner, Annalena (5)
  • Dewhurst, Rian D. (3)
  • Fantuzzi, Felipe (3)
  • Arrowsmith, Merle (2)
  • Hagspiel, Stephan (2)
  • Lamprecht, Anna (2)
  • Lindl, Felix (2)
  • Prieschl, Dominic (2)
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  • Institut für Anorganische Chemie (5)
  • Institut für Physikalische und Theoretische Chemie (1)

EU-Project number / Contract (GA) number

  • 669054 (1)

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Boron- versus Nitrogen-Centered Nucleophilic Reactivity of (Cyano)hydroboryl Anions: Synthesis of Cyano(hydro)organoboranes and 2-Aza-1,4-diborabutatrienes (2021)
Gärtner, Annalena ; Marek, Matthäus ; Arrowsmith, Merle ; Auerhammer, Dominic ; Radacki, Krzysztof ; Prieschl, Dominic ; Dewhurst, Rian D. ; Braunschweig, Holger
Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes.
Adducts of the parent boraphosphaketene H\(_2\)BPCO and their decarbonylative insertion chemistry (2021)
Hagspiel, Stephan ; Fantuzzi, Felipe ; Dewhurst, Rian D. ; Gärtner, Annalena ; Lindl, Felix ; Lamprecht, Anna ; Braunschweig, Holger
The first examples of Lewis base adducts of the parent boraphosphaketene (H\(_2\)B-PCO) and their cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B−C bond of a borole, forming very rare examples of 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals.
A neutral beryllium(I) radical (2021)
Czernetzki, Corinna ; Arrowsmith, Merle ; Fantuzzi, Felipe ; Gärtner, Annalena ; Tröster, Tobias ; Krummenacher, Ivo ; Schorr, Fabian ; Braunschweig, Holger
The reduction of a cyclic alkyl(amino)carbene (CAAC)-stabilized organoberyllium chloride yields the first neutral beryllium radical, which was characterized by EPR, IR, UV/Vis spectroscopy and X-ray crystallography. DFT calculations show significant spin density at beryllium and confirm donor–acceptor bonding between an alkylberyllium radical fragment and a neutral CAAC ligand.
Reaction of Dihalodiboranes(4) with N-Heterocyclic Silylenes: Facile Construction of 1-Aryl-2-Silyl-1,2-Diboraindanes (2017)
Braunschweig, Holger ; Brückner, Tobias ; Deißenberger, Andrea ; Dewhurst, Rian ; Gackstatter, Annika ; Gärtner, Annalena ; Hofmann, Alexander ; Kupfer, Thomas ; Prieschl, Dominic ; Thiess, Torsten ; Wang, Sunewang Rixin
Dihalodiboranes(4) react with an N-heterocyclic silylene (NHSi) to generate NHSi-adducts of 1-aryl-2-silyl-1,2-diboraindanes as confirmed by X-ray crystallography, featuring the functionalization of both B–X (X = halogen) bonds and a C–H bond under mild conditions. Coordination of a third NHSi to the proposed 1,1-diaryl- 2,2-disilyldiborane(4) intermediates, generated by a two-fold B–X insertion, may be crucial for the C–H borylation that leads to the final products. Notably, our results demonstrate the first C–H borylation with a strong B–F bond activated by silylene insertion.
Addukte des Stammboraphosphaketens H\(_{2}\)BPCO und deren Insertionsreaktionen mittels Decarbonylierung (2021)
Hagspiel, Stephan ; Fantuzzi, Felipe ; Dewhurst, Rian D. ; Gärtner, Annalena ; Lindl, Felix ; Lamprecht, Anna ; Braunschweig, Holger
Die ersten Beispiele für Lewis-Basen-Addukte des Stammboraphosphaketens H\(_{2}\)B-PCO und ihre cyclischen Dimere wurden hergestellt. Eines dieser Addukte zeigt unter milden Bedingungen eine Decarbonylierung und anschließende Insertion des Phosphinidens in die B-C-Bindung eines Borols, was in der Bildung sehr seltener Beispiele für 1,2-Phosphaborinine, B,P-Isostere von Benzol, resultiert. Die starken Donoreigenschaften dieser 1,2-Phosphaborinine wurden durch die Synthese ihrer π-Komplexe mit Metallen der Gruppe 6 bestätigt.
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