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The first isolable Ge5-spiropentadiene 1 was synthesized via the reduction of (iPr3Si)2NGeCl (3) with potassium. The crystal structure of 1 reveals a spirocyclic Ge5 skeleton containing two Ge-Ge double bonds (avg. 2.34 A), which are fettered in two Ge3 rings with a dihedral angle of 70.193°. The DFT calculations and orbital analysis show that the σ-delocalization of the Ge5 skeleton and the 2π-delocalized aromatic Ge3 rings enhance the stability of molecule 1.

A new stable six-membered cyclic germylene radical C (•L3Ge:; •L3 = •[CH3C(PhCN–Dip)2]2–, where Dip = 2,6-iPr2C6H3) has been synthesized and structurally characterized. Unlike the germanium-centere...

A new digermylene has been synthesized through the reaction of a six-membered cyclic radical germylene precursor with a mixture of CoBr2 and a seven-membered N-heterocyclic carbene. The density functional theory simulation on the geometry of the digermylene agrees well with the experimental X-ray diffraction result. The digermylene possesses the shortest GeI–GeI bond [2.4853(6) A] compared to the known singly bonded analogues, which can be attributed to σ → π* conjugation. In addition, it is revealed that a stable dative bond cannot form for the reductive radical germylene with the oxidative metal centers.