SiSi Double Bonds: Synthesis of an NHC‐Stabilized Disilavinylidene

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AbstractAn efficient two‐step synthesis of the first NHC‐stabilized disilavinylidene (Z)‐(SIdipp)SiSi(Br)Tbb (2; SIdipp=C[N(C6H3‐2,6‐iPr2)CH2]2, Tbb=C6H2‐2,6‐[CH(SiMe3)2]2‐4‐tBu, NHC=N‐heterocyclic carbene) is reported. The first step of the procedure involved a 2:1 reaction of SiBr2(SIdipp) with the 1,2‐dibromodisilene (E)‐Tbb(Br)SiSi(Br)Tbb at 100 °C, which afforded selectively an unprecedented NHC‐stabilized bromo(silyl)silylene, namely SiBr(SiBr2Tbb)(SIdipp) (1). Alternatively, compound 1 could be obtained from the 2:1 reaction of SiBr2(SIdipp) with LiTbb at low temperature. 1 was then selectively reduced with C8K to give the NHC‐stabilized disilavinylidene 2. Both low‐valent silicon compounds were comprehensively characterized by X‐ray diffraction analysis, multinuclear NMR spectroscopy, and elemental analyses. Additionally, the electronic structure of 2 was studied by various quantum‐chemical methods.