β‐Diketiminato–Germylene Complexes of Carbonyl Ruthenium: Synthesis, Structure, and Reactivity

摘要

> The reaction of the β‐diketiminatochlorogermylene L(Cl)Ge { 1 , L = HC[C(Me)N‐2,6‐ i Pr ₂ C ₆ H ₃ ] ₂ } with Ru ₃ (CO) ₁₂ in molar ratios of 3:1 or 6:1 led to the Ge ₂ Ru complex [L(Cl)Ge] ₂ Ru(CO) ₃ ( 3 ). A speculative GeRu intermediate, L(Cl)GeRu(CO) ₄ , was detected when the reaction was monitored by 1 H NMR spectroscopy at elevated temperatures. The formation of this intermediate was supported by similar monitoring of the reaction of L(PhC≡C)Ge ( 2 ) with Ru ₃ (CO) ₁₂ by 1 H NMR spectroscopy and the isolation of a mixture of L(PhC≡C)GeRu(CO) ₄ ( 4 ) and [L(R)Ge] ₂ Ru(CO) ₃ ( 5 ) from this reaction in a molar ratio of 3:1 as well as the clean formation of 5 from such a reaction in a 6:1 molar ratio. Complex 3 reacted with LiHBEt ₃ through an unusual Cl/Et metathesis to give L(Et)GeRu(CO) ₄ ( 6 ). However, the reaction of 3 with LiN(SiMe ₃ ) ₂ resulted in the base‐assisted dehydrochlorination involving one methyl group of each L ligand backbone and the chlorine atom at the Ge center to yield [L′Ge] ₂ Ru(CO) ₃ {