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

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 { 7 , L′ = HC[C(Me)N‐2,6‐ i Pr 2 C 6 H 3 ][C(CH 2 )N‐2,6‐ i Pr 2 C 6 H 3 ]}. The further reaction of 7 with a stoichiometric amount of H 2 O afforded L(HO)GeRu(CO) 4 ( 8 ) through a 1,4‐dipolar addition across the L′Ge functionality. In addition, the reaction of 3 with I 2 occurred through an oxidative addition at the Ru center to generate L(Cl)GeRuI 2 (CO) 3 ( 10 ).