An Isolable Germylyne Radical with a One-coordinate Germanium Atom
Dongmin Wang1, Cai Zhai2, Yizhen Chen1, Yuhao He1, Xiao-dan Chen3, Shanle Wang1, Lili Zhao2,*, Gernot Frenking2,4,*, Xinping Wang5, and Gengwen Tan1,6,*
1 Soochow Univ, Coll Chem Chem Engn & Mat Sci, Innovat Ctr Chem Sci, Suzhou, Peoples R China
2 Nanjing Tech Univ, Jiangsu Natl Synerget Innovat Ctr Adv Mat, Sch Chem & Mol Engn, Inst Adv Synth, Nanjing, Peoples R China
3 Jinan Univ, Coll Chem & Mat, Guangzhou, Peoples R China
4 Philipps Univ Marburg, Fachbereich Chem, Marburg, Germany
5 Nanjing Univ, Collaborat Innovat Ctr Adv Microstruct, Sch Chem & Chem Engn, State Key Lab Coordinat Chem,Jiangsu Key Lab Adv, Nanjing, Jiangsu, Peoples R China
6 Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin, Peoples R China
Nat. Chem.2022
Carbynes (R-˙C:), 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: 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.
Link：https://www.nature.com/articles/s41557-022-01081-1#citeas
