Persistent Antimony- and Bismuth-Centered Radicals in Solution†
Corresponding Author
Dr. Shintaro Ishida
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)Search for more papers by this authorFumiya Hirakawa
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Search for more papers by this authorProf. Dr. Ko Furukawa
Center for Instrumental Analysis, Institute for Research Promotion, Niigata University, Niigata 950-2181 (Japan)
Search for more papers by this authorDr. Kenji Yoza
Bruker AXS K.K. 3-9 Moriya-cho, Kanagawa-ku, Yokohama 221-0022 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Takeaki Iwamoto
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)Search for more papers by this authorCorresponding Author
Dr. Shintaro Ishida
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)Search for more papers by this authorFumiya Hirakawa
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Search for more papers by this authorProf. Dr. Ko Furukawa
Center for Instrumental Analysis, Institute for Research Promotion, Niigata University, Niigata 950-2181 (Japan)
Search for more papers by this authorDr. Kenji Yoza
Bruker AXS K.K. 3-9 Moriya-cho, Kanagawa-ku, Yokohama 221-0022 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Takeaki Iwamoto
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 (Japan)Search for more papers by this authorThis work was supported in part by the JSPS KAKENHI Grant Number 25708004 (to S.I.), MEXT KAKENHI (Grant-in-Aid for Scientific Research on Innovative Areas “Stimuli-responsive Chemical Species”) Grant Number 24109004 (to T.I.), and a Grant-in-Aid for JSPS Fellows 252439 (to F.H.).
Abstract
Stibinyl and bismuthinyl radicals are recognized as representative intermediates of antimony and bismuth compounds, but still elusive in the condensed phase. We successfully synthesized persistent stibinyl and bismuthinyl radicals in solution by facile dissociation of the corresponding dimers with bulky substituents. We characterized the radicals by NMR and UV/Vis spectroscopy and estimated the thermodynamic parameters for the dissociation equilibria. The radicals show n→p (HOMO→SOMO) transition bands at 497 nm (stibinyl) and 543 nm (bismuthinyl) in 3-methylpentane and react with a stable nitroxyl radical to give the cross-radical coupling products in good yields.
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