CYCLOPENTADIENYL THIOCARBONYL COMPLEXES OF IRON - [CP-STAR-FE(CO)2CS]+, CP-STAR-2FE2(CO)2(CS)2, CP2FE2(CO)3(CS), AND CP2FE2(CO)2(CS)2

Nucleophiles generally react with the new iron thiocarbonyl complex [Cp{black star}Fe(CO)2(CS)]+ (Cp{black star} = η-C5Me5) by attacking at the carbon of the CS ligand. Thus, SMe- gives the dithioester, Cp{black star}Fe(CO)2[(CS)SMe] and N3- gives N-bound thiocyanate, Cp{black star}Fe(CO)2(NCS). It is observed that MeO- attacks initially at the carbon of the CO ligand but more slowly migrates to the carbon of the CS ligand giving Cp{black star}Fe(CO)2[C(S)OMe]. The reaction of the thioesters with MeOSO2CF3 yields the thiocarbene complexes, {Cp{black star}(CO)2Fe[C(SMe)X]}+ (X = OMe, SMe). The thiocarbonyl dimer, Cp{black star}2Fe2(CO)2(CS)2, is synthesized by reduction of [Cp{black star}Fe(CO)2(CS)]+ with NaH. Reactions of Cp2Fe2(CO)3(CS) and Cp2Fe2(CO)2(CS)2 with Raney Ni result in the conversion of the bridging CS ligands to μ-CH2 groups in the complexes Cp2Fe2(CO)3(μ-CH2), Cp2Fe2(CO)2(CS)(μ-CH2) and Cp2Fe2(CO)2(μ-CH2)2. The thiocarbonyl dimers also react with AgBF4 to give [Cp2Fe2(CO)2(CS)2]Ag+ BF4- and {[Cp2Fe2(CO)3(CS)]3Ag}BF4; the structure of the latter compound was determined by X-ray crystallography. © 1990.