Synthesis and Structural Characterization of Metallogermylenes, Cp-Substituted Germylene, and a Germanium(II)-Borane Adduct from Pyridyl-1-azaallyl Germanium(II) Chloride

Abstract

The reaction of [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}GeCl] (1) with Na[M(η5-C5H5)(CO)3]·2DME (M = Mo, W) afforded the metallogermylenes [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Ge-M(η5-C5H5)(CO)3] (M = Mo (2), W (3)). Compounds 2 and 3 have been characterized by X-ray crystallography and NMR and IR spectroscopy. Structural analyses of compounds 2 and 3 are consistent with the presence of lone-pair electrons at the germanium(II) center. The Ge–Mo and Ge–W bond distances of 2.875(1) and 2.852(1) Å are consistent with Ge–metal single bonds. The chlorogermylene 1 was also used in the synthesis of a substituted germylene, [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Ge(η1-C5H5)] (4), by reaction with sodium cyclopentadienylide. The reaction of compound 1 with tris(pentafluorophenyl)borane led to the formation of a Lewis acid–base adduct, [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Ge(Cl)→B(C6F5)3] (5).