Insertion Reaction of Me 3 SiN 3 with Bis(germylene).

Herein, we describe the redox reaction of bis(germylene) PhC(N t Bu) 2 Ge-Ge(N t Bu) 2 CPh with different equivalents of Me 3 SiN 3 affording two distinct products. The reaction of Me 3 SiN 3 with bis-germylene in a 1:1 molar ratio results in compound 1 at -78 °C; however, treatment of bis-germylene with a 2.1 equiv of Me 3 SiN 3 at room temperature results in compound 2 . The formation of 1 and 2 can be rationalized by two successive 3 + 1 cycloadditions of Me 3 SiN 3 with the germanium center of bis(germylene) and N 2 elimination. All of the compounds are well-characterized by various spectroscopic techniques and single-crystal X-ray structural analyses. Density functional theory (DFT) calculations suggest that compound 2 has a dicoordinated nitrogen atom, which is stabilized by hyperconjugative interactions, resulting in pseudo-germylimine moiety. However, the dicoordinated nitrogen atom shows high basicity as indicated by proton affinity values. These are rare examples of isolated products that show insertion as well as simultaneous redox properties of bis(germylene).