Insertion Reactions of NH₃ and H₂O with the Ferriogermylenes ArGeFeCp(CO)₂ (Ar = Ar^Me6 (−C₆H₃‑(C₆H₂‑2,4,6-Me₃)₂) or Ar^iPr4 (−C₆H₃‑(C₆H₃‑2,6‑ⁱPr₂)₂); Cp = η⁵‑C₅H₅): Structural Isomerism and Polymorphism in a Metallogermylene

The ferriogermylenes ArGeFeCp­(CO)₂ (Ar = −C₆H₃-(C₆H₂-2,4,6-Me₃)₂ (Ar^Me6 (1a)), Ar = −C₆H₃-(C₆H₃-2,6-ⁱPr₂)₂ (Ar^iPr4 (1b))) (Cp = η⁵-C₅H₅) react with an excess of NH₃(l) to form the insertion products ArGe­(NH₂)­(H)­FeCp­(CO)₂ (Ar = Ar^Me6 (2a) or Ar^iPr4 (2b)). Similarly, ferriogermylene 1a reacts with water to form the insertion product Ar^Me6Ge­(OH)­(H)­FeCp­(CO)₂ (3). Unusually, crystals of 1a exist as three different polymorphs whose structures differ primarily in their C_ipso–Ge–Fe bond angles. Complexes 1–3 were characterized by NMR, UV–vis, IR spectroscopy, and X-ray crystallography.