Synthesis, Structure and Electronic Properties of a Stable π‐Type 3‐Electron‐2‐Center‐Bonded Species: A Silicon Analogue of a Bicyclo[1.1.0]butane Radical Anion

σ-Type 3-electron-2-center (3e-2c) bonds have been extensively studied as one of the key bonding motifs in radical chemistry and some biological systems. "π-Type 3e-2c-bonded species" that contain a 3e-2c π-bond without an underlying σ-bond framework, however, have been unexplored so far both theoretically and experimentally. Herein, we report the synthesis of the first stable π-type 3e-2c-bonded species, a silicon analogue of a bicyclo[1.1.0]butane radical anion. This compound exhibits an extremely long bridgehead Si-Si bond (3.0638(8) Å) and a strong near-IR absorption at 922 nm in solution which arises from a HOMO→SOMO [π(Si-Si)→π*(Si-Si)] transition. DFT calculations revealed a π-type bonding interaction between the two bridgehead silicon atoms with an unpaired electron mainly delocalized across the corresponding π*-type orbital, which introduces a novel bonding motif for constructing π-electron systems.