The trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAAC_Me] (cAAC_Me=:C(CMe₂)₂(CH₂)NAr, Ar=2,6‐iPr₂C₆H₃) with H₂SiI₂ in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAAC_Me)₂Si:^.]⁺I⁻ (1), which features a cationic cAAC–silicon(I) radical, and [cAAC_Me−H]⁺I⁻. In addition, the reaction of the NHC–iodosilicon(I) dimer [I_Ar(I)Si:]₂ (I_Ar=:C{N(Ar)CH}₂) with 4 equiv of I_Me (:C{N(Me)CMe}₂), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(I_Me)₂SiH]⁺I⁻ (2) comprising the first NHC–parent‐silyliumylidene cation. Its further reaction with fluorobenzene afforded the C_Ar−H bond activation product [1‐F‐2‐I_Me‐C₆H₄]⁺I⁻ (3). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1. Compounds 1–3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X‐ray crystallography.

中文翻译：

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用卡宾捕获硅（I）自由基：阳离子cAAC-硅（I）自由基和NHC-母体-亚甲硅烷基阳离子

描述了用N-杂环卡宾捕获硅（I）自由基的方法。环状（烷基）（氨基）卡宾[cAAC _Me ]（cAAC _Me =：C（CMe ₂）₂（CH ₂）NAr，Ar = 2.6，i Pr ₂ C ₆ H ₃）与H _2的反应在DME中摩尔比为3：1的SiI ₂提供了分离的离子对[（cAAC _Me）₂ Si：的混合物^。] ⁺我^- （1），其特点是阳离子CAAC -硅（I）基团，和[CAAC_我-H] ⁺我^-。此外，NHC-碘硅（I）二聚体[I _Ar（I）Si：] ₂（I _Ar =：C {N（Ar）CH} ₂）与4当量的I _Me（：C {N （Me）的CME} ₂），其通过硅（I）基团的中间体，得到[（I形成进行_我）₂的SiH] ⁺我^- （2包括第一NHC-父- silyliumylidene阳离子）。它与氟苯的进一步反应得到C _Ar -H键活化产物[1-F-2-I _Me - C ₆ H ₄ ] ⁺ I⁻（3）。2和3的分离证实了形成1的反应机理。化合物1 - 3通过EPR和NMR光谱，DFT计算，和X-射线晶体学分析。