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 language | English |
|---|---|
| Pages (from-to) | 253-258 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 26 |
| Issue number | 2 |
| Publication status | Published - 1987 |
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- 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 journal › Article
}
TY - JOUR
T1 - Nineteen-electron adducts in the photochemistry of Cp2Fe2(CO)4 (Cp = η5-C5H5)
AU - Goldman, Alan S
AU - Tyler, David R.
PY - 1987
Y1 - 1987
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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M3 - Article
VL - 26
SP - 253
EP - 258
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 2
ER -