The reaction of the bis(imidazoliumyl)‐substituted P^I cation [(2‐Im^Dipp)P(4‐Im^Dipp)]⁺ (10⁺) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐Im^Dipp)PH(4‐Im^Dipp)]²⁺ (11²⁺) and methylated [(2‐Im^Dipp)PMe(4‐Im^Dipp)]²⁺ (12²⁺) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated P^I cation 10⁺ predicted a stable and “bottleable” P‐centered radical dication [(2‐Im^Dipp)P(4‐Im^Dipp)]^2+. (13^2+.). The reaction of 10⁺ with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13^2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom.

中文翻译：

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持久性磷酰基自由基阳离子的合成及EPR / UV / Vis-NIR光谱电化学研究

双咪唑基取代的P ^I 阳离子[（2-Im ^Dipp）P（4-Im ^Dipp）] ⁺（10 ⁺）（2-Im =咪唑-2-基; 4-Im =咪唑- 4-yl; Dipp = 2,6-di-isopropylphenyl）与三氟甲磺酸（HOTf）或三氟甲基磺酸甲酯（MeOTf）产生相应的质子化[（2-Im ^Dipp）PH（4-Im ^Dipp）] ²⁺（11 ^{2 +}）和甲基化[（2-Im ^Dipp）PMe（4-Im ^Dipp）] ²⁺（12 ²⁺）分别。对低配位P ^I 阳离子10 ^+的EPR / UV / Vis-NIR光谱电化学研究预测了稳定且“可装瓶”的P中心自由基^指示[（2-Im ^Dipp）P（4-Im ^Dipp）] ^2+。（13 ^2+。）。反应10 ⁺与亚硝酰盐NO [光学传递函数]产生持久磷烷基自由基二价阳离子13 ^2+。结晶形式的三氟甲磺酸盐。量子化学研究表明，P原子具有异常高的自旋密度。