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

Research output: Contribution to journalArticle

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Abstract

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
Volume383
Issue number1-3
DOIs
Publication statusPublished - 1990 Feb 20

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Carbon Monoxide
Stars
Iron
iron
stars
Ligands
ligands
Dimers
Carbon
carbon
dimers
Nucleophiles
nucleophiles
X ray crystallography
attack
crystallography
X Ray Crystallography

All Science Journal Classification (ASJC) codes

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

Cite this

@article{823ccef39a0440c79e0fdb9a5feba16d,
title = "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",
abstract = "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.",
author = "Choi, {Moon Gun} and Daniels, {Lee M.} and Angelici, {Robert J.}",
year = "1990",
month = "2",
day = "20",
doi = "10.1016/0022-328X(90)85140-T",
language = "English",
volume = "383",
pages = "321--337",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
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}

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

In: Journal of Organometallic Chemistry, Vol. 383, No. 1-3, 20.02.1990, p. 321-337.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Cyclopentadienyl thiocarbonyl complexes of iron

T2 - [Cp{black star}Fe(CO)2CS]+, Cp{black star}2Fe2(CO)2(CS)2, Cp2Fe2(CO)3(CS), and Cp2Fe2(CO)2(CS)2

AU - Choi, Moon Gun

AU - Daniels, Lee M.

AU - Angelici, Robert J.

PY - 1990/2/20

Y1 - 1990/2/20

N2 - 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.

AB - 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.

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