Carbodicarbene σ/π‐Donation Enables a Reactive Two‐Coordinate Germanium(II) Dication

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Abstract
All previously reported Ge(II) dications have remained chemically dormant, their reactivity confined to simple coinage metal coordination—a consequence of cationization‐induced lone pair contraction that renders the Ge center inaccessible to substrates. We report that dual σ/π‐donating carbodicarbene (CDC) ligands directly counteract this contraction, yielding [(CDC) 2 Ge][OTf] 2 ( 4 ), the first two‐coordinate Ge(II) dication to display broad reactivity beyond coinage metal coordination. Crystallographic and computational analysis reveal a delocalized 3c‐4e C‐Ge‐C moiety and a less contracted Ge lone pair with retained Ge‐centered LUMO, underpinning an unprecedented reactivity profile encompassing 1,1‐oxidative addition, [1 + 4] cycloaddition, selenium insertion, and cooperative C–S bond activation. As a Ge‐donor ligand, 4 coordinates to Rh, Ir, and Ag with donor strength comparable to that of IMes and forms geminal bimetallic complex 8 , featuring a rare noncluster Ag–Ge–Ag three‐center two‐electron bonding motif. These results establish CDC‐based low‐coordination stabilization as a productive strategy for accessing structurally simple yet reactive main‐group dications.
Funding Information
  • National Natural Science Foundation of China (22373050)
  • Natural Science Foundation of Jiangsu Province (BK20250032)
  • Academia Sinica (AS‐IA‐113‐M01)

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