%0 Journal Article %1 Roy.2015b %A Roy, Sudipta %A Stueckl, A. Claudia %A Demeshko, Serhiy %A Dittrich, Birger %A Meyer, Jann %A Maity, Bholanath %A Koley, Debasis %A Schwederski, Brigitte %A Kaim, Wolfgang %A Roesky, Herbert W. %D 2015 %J Journal of the American Chemical Society %K diphenylchlorophosphine radical stable trichlorosilane %N 14 %P 4670--4673 %R 10.1021/jacs.5b02403 %T Stable Radicals from Commonly Used Precursors Trichlorosilane and Diphenylchlorophosphine %V 137 %X 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 temp. led to the formation of stable radicals Ph2P-Si(cAAC·)Cl2 (2a,b). Compds. 2a,b were characterized by X-ray single crystal diffraction, mass spectrometry and studied by cyclic voltammetry and theor. calcns. Radical properties of 2 are confirmed by EPR measurements that suggest the radical electron in 2 couples with 14N (I = 1), 35/37Cl (I = 3/2), and 31P (I = 1/2) nuclei leading to multiple hyperfine lines. Hyperfine coupling parameters computed from DFT calcns. are in good agreement with those of exptl. values. Electronic distributions obtained from the theor. calcns. suggest that the radical electron mostly resides on the carbene C of 2. on SciFinder(R)

@article{Roy.2015b, 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 temp. led to the formation of stable radicals Ph2P-Si(cAAC·)Cl2 (2a,b). Compds. 2a,b were characterized by X-ray single crystal diffraction, mass spectrometry and studied by cyclic voltammetry and theor. calcns. Radical properties of 2 are confirmed by EPR measurements that suggest the radical electron in 2 couples with 14N (I = 1), 35/37Cl (I = 3/2), and 31P (I = 1/2) nuclei leading to multiple hyperfine lines. Hyperfine coupling parameters computed from DFT calcns. are in good agreement with those of exptl. values. Electronic distributions obtained from the theor. calcns. suggest that the radical electron mostly resides on the carbene C of 2. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Roy, Sudipta and Stueckl, A. Claudia and Demeshko, Serhiy and Dittrich, Birger and Meyer, Jann and Maity, Bholanath and Koley, Debasis and Schwederski, Brigitte and Kaim, Wolfgang and Roesky, Herbert W.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/25709597807d8b2aefd53359b67e5669a/huebleriac}, doi = {10.1021/jacs.5b02403}, interhash = {e7d5a81fc40bd961e58cd5b7cd2d1bda}, intrahash = {5709597807d8b2aefd53359b67e5669a}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {diphenylchlorophosphine radical stable trichlorosilane}, number = 14, pages = {4670--4673}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Stable Radicals from Commonly Used Precursors Trichlorosilane and Diphenylchlorophosphine}, volume = 137, year = 2015 }