In this study, the isolation, characterization and reactivity of a crystalline germylyne radical using a sterically hindered hydrindacene ligand was reported. The resulting germylyne radical features a one-coordinate germanium atom and exhibits a doublet ground state.
Carbynes (R-C-center dot:), species that bear a monovalent carbon atom with three non-bonding valence electrons, are important intermediates and potentially useful in organic synthetic chemistry. However, free species of the type R-E-center dot: of any group 14 element (E) have eluded isolation in the condensed phase due to their high reactivity. Here we report the isolation, characterization and reactivity of a crystalline germylyne radical by using a sterically hindered hydrindacene ligand. The germylyne radical bears an essentially one-coordinate germanium atom as shown by single-crystal X-ray diffraction analysis. Electron paramagnetic resonance spectroscopic studies and theoretical calculations show that the germylyne radical features a doublet ground state, and the three non-bonding valence electrons at the germanium atom contribute to the lone pair of electrons as the highest occupied molecular orbital-3 and one unpaired electron as the singly occupied molecular orbital.
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