Synthesis and Characterization of Mononuclear Iron Silanethiolato Complexes Containing an Unsupported Fe-S-Si Bond System: X-ray Crystal Structure of CpFe(CO)2SSiPhs and Its Reaction with S02

Mononuclear iron silanethiolato complexes of the type CpFe^C^SSiRs, where R = Ph (la) and ʹPr (1b), were prepared via treatment of [CpFe(CO)2(THF)]BF4 with Li8SiPh3-Et20 and NaSSiʹPrs, respectively. The molecular structure of la was determined by X-ray crystallography. Complex la was reacted with 1 equiv of 802 to give the corresponding O-silyl thiosultite, CpFe(CO)2SS(0)OSiPh3 (2), via 1,2-insertion of 802 into the 8-8i bond. This reaction models the activation of 802 in the homogeneously catalyzed Claus process.