Halogermanium(II) Complexes Having Phenylamidinate As Supporting Ligands: Syntheses, Characterizations, and Reactivities

Novel germylenes [{Me3SiNC(Ph)NSiMe3}GeX] (X = Cl, Br, I) and [{Me3SiNC(Ph)NSiMe3}2Ge] with the bidentate phenylamidinato ligand have been synthesized in high yields by a salt metathesis reaction between Cl2Ge·dioxane or I2Ge and the lithium salt of the ligand. They were characterized by 1H and 13C NMR and mass spectrometry and single-crystal X-ray structure analyses, which confirmed N-chelation and a three-coordinate germanium center. The cycloaddition reactions with o-quinone led to cycloadducts, whose structures were determined by X-ray analyses. The chelation of the ligand to the metal center was conserved, affording penta- and hexacoordinated germanium(IV) atoms. Complexation reactions with [codW(CO)4] and [nbdMo(CO)4] resulted in trinuclear bis(germanium(II)) transition-metal complexes in “trans” octahedral geometry.