Weakly Bound Dimer of a Diaryloxygermylene Derived from a tBuPh2Si-Substituted 2,2′-Methylenediphenol

Novel diaryloxygermylenes have been prepared by the reaction of Lappert’s germylene, Ge[N(SiMe3)2]2, with 2,2′-methylenediphenols bearing different substituents. The bulkiness of the substituents on the ortho positions of the phenolic oxygen (6 and 6′ positions) affects the structure of the products both in the solid-state and in solution. When the ortho substituents are SitBuPh2, the diaryloxygemylene crystalizes as a weakly bound dimer with intermolecular Ge…O distances of ca. 3.0 Å and exists as a monomer in solution. In contrast, the germylene with SiMePh2 groups as the ortho substituents form a tightly bound dimer featuring a Ge2O2 rhombus with cis-oriented terminal aryloxy groups in the crystalline state, which is confirmed to be maintained in solution through the VT (variable-temperature)-1H NMR studies. To the best of our knowledge, the former dimeric structure is unprecedented in the family of dioxytetrylenes.