title: Stable radicals from commonly used precursors trichlorosilane and diphenylchlorophosphine.
abstract: Intermediate species dichlorosilylene was generated in situ from trichlorosilane and inserted into the P-Cl bond of diphenylchlorophosphine (Ph2P-Cl) to obtain Ph2P-SiCl3 (1). Monodechlorination of 1 by cyclic alkyl(amino) carbenes (cAACs)/KC8 in THF at low temperature led to the formation of stable radicals Ph2P-Si(cAAC·)Cl2 (2a,b). Compounds 2a,b were characterized by X-ray single crystal diffraction, mass spectrometry and studied by cyclic voltammetry and theoretical calculations. Radical properties of 2 are confirmed by EPR measurements that suggest the radical electron in 2 couples with (14)N (I = 1), (35/37)Cl (I = 3/2), and (31)P (I = 1/2) nuclei leading to multiple hyperfine lines. Hyperfine coupling parameters computed from DFT calculations are in good agreement with those of experimental values. Electronic distributions obtained from the theoretical calculations suggest that the radical electron mostly resides on the carbene C of 2.
authors: †Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.
authors: Sudipta
authors: S
authors: Roy
authors: †Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.
authors: A Claudia
authors: AC
authors: Stückl
authors: †Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.
authors: Serhiy
authors: S
authors: Demeshko
authors: ‡Institut für Anorganische und Angewandte Chemie, Universität Hamburg, 20146 Hamburg, Germany.
authors: Birger
authors: B
authors: Dittrich
authors: †Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.
authors: Jann
authors: J
authors: Meyer
authors: §Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, West Bengal, India.
authors: Bholanath
authors: B
authors: Maity
authors: §Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, West Bengal, India.
authors: Debasis
authors: D
authors: Koley
authors: ∥Universität Stuttgart, Institut für Anorganische Chemie, 70569 Stuttgart, Germany.
authors: Brigitte
authors: B
authors: Schwederski
authors: ∥Universität Stuttgart, Institut für Anorganische Chemie, 70569 Stuttgart, Germany.
authors: Wolfgang
authors: W
authors: Kaim
authors: †Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany.
authors: Herbert W
authors: HW
authors: Roesky