Nineteen-electron adducts in the photochemistry of Cp2Fe2(CO)4 (Cp = η5-C5H5)

Alan S Goldman, David R. Tyler

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Abstract

Cp2Fe2(CO)4 is apparently different from the other metal-metal-bonded carbonyl dimers in that irradiation of this dimer in the presence of ligands does not lead to disproportionation: Cp2Fe2(CO)4 + L + hv » CpFe(CO)2 - + CpFe(CO)3-nLn +. However, it was demonstrated that with most ligands the disproportionation reaction does occur but the back-reaction of the products is facile. The back-reaction can be prevented by reacting further one of the products. For example, in CH2Cl2 solution, CpFe(CO)2 - reacts with the solvent to give CpFe(CO)2CH2Cl and the back-reaction is prevented. The mechanism of the disproportionation reaction is proposed to be a chain mechanism involving 19-electron adducts formed by the reaction of a 17-electron metal radical with a ligand, e.g. CpFe(CO)2 + L → CpFe(CO)2L. It is demonstrated that the 19-electron adducts are powerful reductants. The following organometallic, organic, and inorganic substrates were reduced by the 19-electron species, thereby demonstrating the versatility of these species as reducing agents: CpMo(CO)3Cl, Fe(CN)6 3-, Mn2(CO)10, Re2(CO)10, Ru3(CO)12, Fe(CO)5, N-n-butylpyridinium, and Cp2Co+. Experiments involving the reduction of Cp2Co+ demonstrated several mechanistic points concerning the reactivity of 19-electron species.

Original languageEnglish
Pages (from-to)253-258
Number of pages6
JournalInorganic Chemistry
Volume26
Issue number2
Publication statusPublished - 1987

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Photochemical reactions
photochemical reactions
adducts
Electrons
Metals
Reducing Agents
Ligands
electrons
Dimers
ligands
dimers
metals
Organometallics
versatility
products
Irradiation
reactivity
Substrates
irradiation
Experiments

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Nineteen-electron adducts in the photochemistry of Cp2Fe2(CO)4 (Cp = η5-C5H5). / Goldman, Alan S; Tyler, David R.

In: Inorganic Chemistry, Vol. 26, No. 2, 1987, p. 253-258.

Research output: Contribution to journalArticle

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N2 - Cp2Fe2(CO)4 is apparently different from the other metal-metal-bonded carbonyl dimers in that irradiation of this dimer in the presence of ligands does not lead to disproportionation: Cp2Fe2(CO)4 + L + hv » CpFe(CO)2 - + CpFe(CO)3-nLn +. However, it was demonstrated that with most ligands the disproportionation reaction does occur but the back-reaction of the products is facile. The back-reaction can be prevented by reacting further one of the products. For example, in CH2Cl2 solution, CpFe(CO)2 - reacts with the solvent to give CpFe(CO)2CH2Cl and the back-reaction is prevented. The mechanism of the disproportionation reaction is proposed to be a chain mechanism involving 19-electron adducts formed by the reaction of a 17-electron metal radical with a ligand, e.g. CpFe(CO)2 + L → CpFe(CO)2L. It is demonstrated that the 19-electron adducts are powerful reductants. The following organometallic, organic, and inorganic substrates were reduced by the 19-electron species, thereby demonstrating the versatility of these species as reducing agents: CpMo(CO)3Cl, Fe(CN)6 3-, Mn2(CO)10, Re2(CO)10, Ru3(CO)12, Fe(CO)5, N-n-butylpyridinium, and Cp2Co+. Experiments involving the reduction of Cp2Co+ demonstrated several mechanistic points concerning the reactivity of 19-electron species.

AB - Cp2Fe2(CO)4 is apparently different from the other metal-metal-bonded carbonyl dimers in that irradiation of this dimer in the presence of ligands does not lead to disproportionation: Cp2Fe2(CO)4 + L + hv » CpFe(CO)2 - + CpFe(CO)3-nLn +. However, it was demonstrated that with most ligands the disproportionation reaction does occur but the back-reaction of the products is facile. The back-reaction can be prevented by reacting further one of the products. For example, in CH2Cl2 solution, CpFe(CO)2 - reacts with the solvent to give CpFe(CO)2CH2Cl and the back-reaction is prevented. The mechanism of the disproportionation reaction is proposed to be a chain mechanism involving 19-electron adducts formed by the reaction of a 17-electron metal radical with a ligand, e.g. CpFe(CO)2 + L → CpFe(CO)2L. It is demonstrated that the 19-electron adducts are powerful reductants. The following organometallic, organic, and inorganic substrates were reduced by the 19-electron species, thereby demonstrating the versatility of these species as reducing agents: CpMo(CO)3Cl, Fe(CN)6 3-, Mn2(CO)10, Re2(CO)10, Ru3(CO)12, Fe(CO)5, N-n-butylpyridinium, and Cp2Co+. Experiments involving the reduction of Cp2Co+ demonstrated several mechanistic points concerning the reactivity of 19-electron species.

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