Synthesis and EPR/UV/Vis-NIR spectroelectrochemical investigation of a persistent phosphanyl radical dication.
Synthesis and EPR/UV/Vis-NIR spectroelectrochemical investigation of a persistent phosphanyl radical dication.
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DOI：
10.1002/anie.201502737
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发表时间：
2015-09
影响因子：
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通讯作者：
K. Schwedtmann;Stephen Schulz;Felix Hennersdorf;T. Strassner;E. Dmitrieva;J. Weigand
中科院分区：
文献类型：
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作者：
K. Schwedtmann;Stephen Schulz;Felix Hennersdorf;T. Strassner;E. Dmitrieva;J. Weigand
双（咪唑磺酰基）取代P(I)阳离子[(2- im (Dipp))P(4-Im(Dipp))](+) (10(+)) （2- im =咪唑-2-基；4-Im=咪唑-4-基；Dipp=2,6-二异丙基苯基）与三氟甲烷磺酸（HOTf）或三氟甲基磺酸甲酯（MeOTf）反应，分别产生相应的质子化[(2- im (Dipp)))PH(4-Im(Dipp))](2+)（11(2+)）和甲基化[(2- im (Dipp))) (4-Im(Dipp))](2+)（12(2+)）表征。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的“可装瓶”P中心自由基[(2- im (Dipp))P(4-Im(Dipp))]（2+）。(13 (2 +))． 10（+）与亚硝基盐NO[OTf]反应生成持久的磷酰自由基13(2+)，形成结晶形式的三氟酸盐。量子化学研究揭示了P原子异常高的自旋密度。
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+) (11(2+) ) and methylated [(2-Im(Dipp) )PMe(4-Im(Dipp) )](2+) (12(2+) ) 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.