Redox Reactions of a Stable Dialkylphosphinyl Radical
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- 作者：Fumiya Hirakawa ; Hitomi Ichikawa ; Shintaro Ishida ; Takeaki Iwamoto
- 刊名：Organometallics
- 出版年：2015
- 出版时间：June 22, 2015
- 年：2015
- 卷：34
- 期：12
- 页码：2714-2716
- 全文大小：205K
- ISSN：1520-6041
文摘
A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P鈥?/sup>), showed both irreversible one-electron oxidation and reduction peaks at 鈭?.24 and 鈭?.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P鈥?/sup> with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]鈭?/sup> and [K(crypt-222)]+[RH2P]鈭?/sup>. Whereas [K(18-c-6)]+[RH2P]鈭?/sup> exists as a contact ion pair, [K(crypt-222)]+[RH2P]鈭?/sup> exists as a solvent-separated ion pair in the solid state. Reaction of RH2P鈥?/sup> with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex.