Excellent yield of a variety of silicon-boron radicals and their reactivity

Mohd Nazish; Yi Ding; Christina M Legendre; Arun Kumar; Nico Graw; Brigitte Schwederski; Regine Herbst-Irmer; Parameswaran Parvathy; Pattiyil Parameswaran; Dietmar Stalke; Wolfgang Kaim; Herbert W Roesky

doi:10.1039/d2dt01318e

Excellent yield of a variety of silicon-boron radicals and their reactivity

Dalton Trans. 2022 Jul 26;51(29):11040-11047. doi: 10.1039/d2dt01318e.

Affiliations

¹ Institut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, Göttingen 37077, Germany. hroesky@gwdg.de.
² Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, Stuttgart 70569, Germany.
³ National Institute of Technology Calicut, Kozhikode, Kerala 673601, India.

PMID: 35796059
DOI: 10.1039/d2dt01318e

Abstract

Herein we report stable silicon-boron radicals of composition LSi(NMe₂)-B(Br)Tip (1), LSi(NMe₂)-B(I)Tip (2) LSi(^tBu)-B(I)Tip (3) [L = PhC(N^tBu)₂]. They were prepared in high yield using a one pot reaction of LSiR, X₂BTip and KC₈ in a 1 : 1 : 1 molar ratio (R = ^tBu, NMe₂; X = Br, I). The reaction of the silicon-boron radical with Br₂ and Se affords the dihalogenated compound LSi(^tBu)-B(Br₂)Tip (4) and oxidative addition product LSi(^tBu)Se (5). All the compounds were characterized by single-crystal X-ray structural analysis, electron paramagnetic resonance (EPR) analysis, elemental analysis, multinuclear NMR spectroscopy, and mass spectrometry. Quantum chemical calculations show that the B-centered radicals 1-3 are stabilised by hyperconjugative interactions.