Synthesis of Silyl–Molybdenum Complexes Connected by a 1,1′-Metallocenylene Unit and Their Electrochemical Properties



Methyl–molybdenum complexes react with hydrosilanes or hydrogermane under photo-irradiation to form the corresponding silyl– or germyl–molybdenum complexes, [(η5-C5Me5)Mo(CO)3(ER3)] [ER3 = SiPh3 (1), GePh3 (2), SiMe2Ph (3), SiMe2(C5H4FeC5H5) (4)]. This method can be adapted to form metallocenylene compounds that bear two dimethylsilyl groups, [{(η5-C5Me5)Mo(CO)3(SiMe2C5H4)}2M] [M = Fe (5), Ru (6)]. All of the new complexes were fully characterized by means of 1H and 13C{1H} NMR spectroscopy and elemental analyses. In addition, the structures of 1, 5, and 6 were determined by single-crystal X-ray diffraction studies. The electrochemical measurements of the ferrocene derivatives that bear one or two {(η5-C5Me5)Mo(CO)3(SiMe2)} substituent(s) revealed that the {(η5-C5Me5)Mo(CO)3(SiMe2)} unit has an electron-donating nature.