持久膦基自由基二阳离子的合成及电子顺磁共振/紫外可见-近红外光谱电化学研究。
Synthesis and EPR/UV/Vis-NIR spectroelectrochemical investigation of a persistent phosphanyl radical dication.
机构信息
TU Dresden, Professur für Anorganische Molekülchemie, 01062 Dresden (Germany).
TU Dresden, Professur für Physikalische Organische Chemie, 01062 Dresden (Germany).
出版信息
Angew Chem Int Ed Engl. 2015 Sep 14;54(38):11054-8. doi: 10.1002/anie.201502737. Epub 2015 Jul 31.
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) ) (11(2+) ) and methylated (2-Im(Dipp) )PMe(4-Im(Dipp) ) (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) ) (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.
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-基；Dipp=2,6-二异丙基苯基）与三氟甲磺酸（HOTf）或甲基三氟甲磺酸酯（MeOTf）反应，分别生成相应的质子化 (2-Im(Dipp) )PH(4-Im(Dipp) ) (11(2+) )和甲基化 (2-Im(Dipp) )PMe(4-Im(Dipp) ) (12(2+) )二阳离子。对低配位 P(I) 阳离子 10(+) 的电子顺磁共振/紫外可见-近红外光谱电化学研究预测了一种稳定的、“可瓶装”的 P 中心自由基二阳离子 (2-Im(Dipp) )P(4-Im(Dipp) ) (13(2+.) )。10(+)与亚硝酰盐 NO[OTf]的反应以结晶形式生成持久的膦自由基二阳离子 13(2+.)作为三氟甲酸盐。量子化学研究表明 P 原子的自旋密度异常高。
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