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

doi:10.1016/0022-328X(90)85140-T

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

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 language	English
Pages (from-to)	321-337
Number of pages	17
Journal	Journal of Organometallic Chemistry
Volume	383
Issue number	1-3
DOIs	https://doi.org/10.1016/0022-328X(90)85140-T
Publication status	Published - 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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10.1016/0022-328X(90)85140-T

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.}",

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.",

year = "1990",

month = feb,

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",

number = "1-3",

}

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.

N1 - 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.

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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