Cyclopentadienyl thiocarbonyl complexes of iron: [Cp{black star}Fe(CO)2CS]+, Cp{black star}2Fe2(CO)2(CS)2, Cp2Fe2(CO)3(CS), and Cp2Fe2(CO)2(CS)2

Moon Gun Choi, Lee M. Daniels, Robert J. Angelici

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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.

Original languageEnglish
Pages (from-to)321-337
Number of pages17
JournalJournal of Organometallic Chemistry
Issue number1-3
Publication statusPublished - 1990 Feb 20

Bibliographical note

Funding Information:
help of Dr. R.D. Scott in obtaining the temperature-dependent NMR data. Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under contract No. W-740%Eng-82. This research was supported by the Office of Basic Energy Sciences, Chemical Sciences Division.

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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