Synthesis and Complexation of a Free Germanide Bearing a Tridentate N-Heterocyclic Substituent

The tris-N-heterocycle germanide (tmim)Ge^- (1) (tmimH₃ = tris(3-methylindol-2-yl)methane) was synthesized by nucleophilic substitution for the tmim^3- trianion on GeCl₂·dioxane. In combination with the previously reported (tmim)Si^- and (tmim)P analogues, it provides a convenient model for investigating the influence of the central atom on the properties of isoelectronic ligands. Complexation of the germanide (tmim)Ge^- to CuCl resulted in the dimeric chloro cuprate [(tmim)GeCu(μ-Cl)]₂ ^2-, which is prone to dissociation in MeCN to form the neutral, solvated germylcopper (tmim)GeCu(NCMe)₃. The reaction of 1 with Fe₂(CO)₉ afforded the germyl iron tetracarbonyl [(tmim)GeFe(CO)₄]^-. Analysis of the ν̃(CO) infrared absorption bands in this complex indicates that the combined electron donating and accepting properties of 1 are found in between those of (tmim)P and (tmim)Si^-. In contrast to (tmim)Si^-, (tmim)Ge^- is reluctant to coordinate to FeCl₂, likely because of its softer Lewis base character. Key structural features of the ligands and complexes reflect changes in their electronic properties. In particular, the N-Ge-N angles increase upon coordination to a metal fragment, suggesting increasing hybridization of the Ge s- and p-orbitals. These findings will be useful in further understanding low-valent heavier group 14 complexes in organometallic chemistry.