| Autor: |
Nazish M; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Legendre CM; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Sarkar SK; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Lücken J; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Goffitzer DJ; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, Frankfurt am Main 60438, Germany., Diefenbach M; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, Frankfurt am Main 60438, Germany., Schwederski B; Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany., Herbst-Irmer R; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Stalke D; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany., Holthausen MC; Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, Frankfurt am Main 60438, Germany., Kaim W; Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany., Roesky HW; Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany. |
| Abstrakt: |
Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of Br 2 BTip (Tip = 2,4,6- i PrC 6 H 2 ) with KC 8 in the presence of LSi-R affords LSi( t Bu)-B(Br)Tip ( 1 ) and LSi(N(TMS) 2 )-B(Br)Tip ( 2 ) [L = PhC(N t Bu) 2 ]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms. 1 and 2 exhibit extraordinary stability to high temperatures under inert conditions in solution and air stability in the solid state. Both radicals have been isolated and fully characterized by electron paramagnetic resonance spectroscopy, SQUID magnetometry, mass spectrometry, cyclic voltammetry, single-crystal X-ray structure analysis, and density functional theory calculations. Moreover, compound 1 exhibits one-electron transfer when treated with 1 equiv of AgSO 3 CF 3 and [Ph 3 C] + [B(C 6 F 5 ) 4 ] - , respectively, resulting in the corresponding cations [LSi( t Bu)-B(Br)Tip] + [CF 3 SO 3 ] - ( 3 ) and [LSi( t Bu)-B(Br)Tip] + [B(C 6 F 5 ) 4 ] - ( 4 ). Compounds 3 and 4 have been characterized with multinuclear NMR and mass spectrometry. |
