Abstrakt
Hydrogen sulfide reacts with tucked-in titanocene complexes [Ti(III){η5:η1-C5Me4(CH2)}Cp*] (Cp* = η5-C5Me5) (2) and [Ti{η4:η3-C5Me3(CH2)2}Cp*] (3) and their precursors [Cp*2TiMe] (2a) and [Cp*2Ti(η2-Me3SiCIDENTICAL TOCSiMe3)] (3a), respectively, to give the corresponding titanocene hydrosulfides [Cp*2Ti(SH)] (4) and [Cp*2Ti(SH)2] (1), respectively. Hydrogen sulfide also cleaves intramolecular σ- or π-TiMINUS SIGN C bonds in ansa-[TiIII(η1:η5:η5-C5Me4SiMe2CHCH2SiMe2C5Me4)] (5) and ansa-[TiII(η2:η5:η5-C5Me4SiMe2CH=CHSiMe2C5Me4)] (6), affording hydrosulfides ansa-[(η5-CH2Me2SiC5Me4)2Ti(SH)] (7) and ansa-[(η5-CH2Me2SiC5Me4)2Ti(SH)2] (8).
The SMINUS SIGN H bonds of hydrosulfides 4 and 7 were able to react with the TiMINUS SIGN C bonds in 2 and 5, affording titanocene sulfides [(Cp*2TiIII)2S] (11) and ansa-[{(η5-CH2Me2SiC5Me4)2TiIII}2S] (12), respectively. Combination of 7 with 2a gave rise to the mixed titanocene sulfide [ansa-{(η5-CH2SiMe2C5Me4)2Ti}S(TiCp*2)] (13).