Synthesis and Properties of the First Stable Germabenzene

The first stable germabenzene (1a) bearing an efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, was successfully synthesized by the reaction of the corresponding chlorogermane (4) with lithium diisopropylamide in THF. The molecular structure and aromaticity of 1a were discussed on the basis of its NMR, UV−vis, and Raman spectra, X-ray crystallographic analysis, and theoretical calculations. All 1H and 13C NMR chemical shifts of the germabenzene ring of 1a were in good agreement with those calculated. UV−vis and Raman spectra of 1a showed patterns similar to those of benzene, suggesting the structural similarity between germabenzene and benzene. X-ray crystallographic analysis of 1a revealed that the germabenzene ring was almost planar, indicating the delocalization of π-electrons. Theoretical calculations (NICS(1) and ASEisom) also indicated the ring current effects and aromatic stabilization of the germabenzene. While germabenzene 1a reacted as a Ge−C double-bond compound (germene) with mesitonitrile oxide and 2,3-dimethyl-1,3-butadiene, 1a also reacted as a 1-germabuta-1,3-diene with C−C double- and triple-bond compounds. Furthermore, 1a reacted with water and MeOH to give both 1, 2- and 1, 4-adducts.