Synthesis and Characterization of Ruthenium Germyl Complexes with Various Substituents

Reactions of dichlorogermyl ruthenium complexes(PPh3)(X)RuGeCl2ArTrip(X=H,1;Cl,2;ArTrip=C6H3-2-(η6-Trip)-6-Trip,Trip=2,4,6-iPr3-C6H3)with various reagents,including Grignard reagent,LiHBEt3 and Na/naphthalene were investigated,realizing the substituent modulation on Ge and Ru atoms.1 reacted with EtMgBr forming(PPh3)HRu-GeBr2ArTrip(3)and(PPh3)HRuGeEt2ArTrip(4)depending on the reaction temperature.The reaction of 1 with LiHBEt3 also resulted in the formation of 4,where LiHBEt3 acted as ethyl transfer reagent instead of hydrogenation reagent.Additionally,1 reacted with HBF4 afforded ionic product[(PPh3)H2RuGeCl2ArTrip][BF4](5).On the other hand,reduction of 2 with Na/naphthalene produced dihydroxyl complex(PPh3)HRuGe(OH)2ArTrip(6),while the reaction with I2 underwent monoiodination on Ru with the formation of(PPh3)IRuGeCl2ArTrip(7).All compounds were fully characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction.