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

Reaction of the -diketiminato cholorogermylene L(Cl)Ge (L = HC[C(Me)N-2,6-iPr2C6H3]2, 1) with Ru3(CO)12 in a molar ratio of either 3:1 or 6:1 both led to the Ge2Ru complex [L(Cl)Ge]2Ru(CO)3 (3). A speculative GeRu intermediate L(Cl)GeRu(CO)4 could be detected when the reaction at varied elevated temperatures was monitored by 1H NMR, which was supported by similar 1H NMR monitoring for the reaction of L(PhC≡C)Ge (2) with Ru3(CO)12 and the isolation of a mixture of L(PhC≡C)GeRu(CO)4 (4) and [L(R)Ge]2Ru(CO)3 (5) from the latter reaction in a molar ratio of 3:1, as well as the clean formation of 5 from such reaction in the 6:1 molar ratio. 3 reacted with LiHBEt3 through an unusual Cl/Et metathesis to give compound L(Et)GeRu(CO)4 (6). The reaction of 3 with LiN(SiMe3)2, however, resulted in the base-assisted dehydrochlorination involving one methyl group on each L ligand backbone and the chloride at the Ge center to yield [L′Ge]2Ru(CO)3 (7, L′ = HC[C(Me)N-2,6-iPr2C6H3][C(CH2)N-2,6-iPr2C6H3]). Further reaction of 7 with stoichiometric amonut of H2O afforded L(HO)GeRu(CO)4 (8) via a 1,4-dipolar addition across the L′Ge functionality. In addition, reaction of 3 with I2 occurred by an oxidative addition at the Ru to generate L(Cl)GeRuI2(CO)3 (10).