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

Abstract

Two iminocarboranyl germylenes, 1,2-[C(tBu)=N(Dipp)Ge(Cl)]-1,2-C2B10H10 (2) (Dipp = 2,6-iPr2C6H3) and [1-{C(tBu)=N(Dipp)}-1,2-C2B10H10]2Ge (3), have been prepared and structurally characterized. The reaction of 2 with Me3NO or S8 afforded the germanium oxygen- or sulfur-bridged dimer [1-{C(tBu)=N(Dipp)-1,2-C2B10H10}Ge(µ-O)(Cl)]2 (4) or [1-{C(tBu)=N(Dipp)-1,2-C2B10H10}Ge(µ-S)(Cl)]2 (5) containing a four-membered Ge2O2 or Ge2S2 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(tBu)=N(Dipp)Ge[Fe(Cp)(CO)2]}-1,2-C2B10H10 (6). All new compounds were characterized by multiple NMR spectroscopic techniques and single-crystal X-ray analysis.