Synthesis and Characterization of an Eclipsed Digermylene as a Building Block to Construct a Cyclic Octagermylene

The preparation of an unprecedented Ge^I‐Ge^I bonded digermylene K₂{Ge₂(μ‐κ²:η²:η⁴‐2,6‐(2,6‐ⁱPr₂C₆H₃‐N)₂‐4‐CH₃C₅H₂N)₂}] in an eclipsed conformation stabilized by two bridging diamidopyridyl ligands is presented. Although it exhibits an eclipsed conformation, the Ge?Ge bond length is 2.5168(6) Å, which is shorter than those in the trans ‐bent and gauche digermylenes. In combination with two pendant amido groups, the Ge^I₂ motif is employed as a building block to assemble the first example of octagermylene Ge₄(μ‐κ²:κ¹‐2,6‐(2,6‐ⁱPr₂C₆H₃‐N)₂‐4‐CH₃C₅H₂N)₂]₂ showing a cyclic configuration and containing three distinct types of Ge^I?Ge^I bonds.