Synthesis, Structure, and Reactivity of Carboranyl‐Supported Germylenes: Approaching Germanones

摘要

> Two iminocarboranyl germylenes, 1,2‐[C( t Bu)=N(Dipp)Ge(Cl)]‐1,2‐C ₂ B ₁₀ H ₁₀ ( 2 ) (Dipp = 2,6‐ i Pr ₂ C ₆ H ₃ ) and [1‐{C( t Bu)=N(Dipp)}‐1,2‐C ₂ B ₁₀ H ₁₀ ] ₂ Ge ( 3 ), have been prepared and structurally characterized. The reaction of 2 with Me ₃ NO or S ₈ afforded the germanium oxygen‐ or sulfur‐bridged dimer [1‐{C( t Bu)=N(Dipp)‐1,2‐C ₂ B ₁₀ H ₁₀ }Ge(μ‐O)(Cl)] ₂ ( 4 ) or [1‐{C( t Bu)=N(Dipp)‐1,2‐C ₂ B ₁₀ H ₁₀ }Ge(μ‐S)(Cl)] ₂ ( 5 ) containing a four‐membered Ge ₂ O ₂ or Ge ₂ S ₂ ring, respectively. On the other hand, the reaction of 2 with K[CpFe(CO) ₂ ] led to the isolation of an iron–germylene compound featuring a Ge–Fe σ bond, 1,2‐{C( t Bu)=N(Dipp)Ge[Fe(Cp)(CO) ₂ ]}‐1,2‐C ₂ B ₁₀ H ₁₀ ( 6 ). All new compounds were characterized by multiple NMR sp