Photochemistry of π-cyclopentadienylcarbonylmetal halides in dimethyl sulphoxide and related solvents
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 14,p. 1475-1478
- https://doi.org/10.1039/dt9730001475
Abstract
The principal product when solutions in dimethyl sulphoxide or pyridine of π-cyclopentadienylcarbonylmetal halides of Fe, Mo, and W are irradiated at long wavelengths (λ > 400 nm) is a dimer: this is [(π-C5H5)Fe(CO)2]2 in the case of Fe (indicating loss of halogen) but appears to be [(π-C5H5)M(CO)2Cl]2 for Mo and W; free cyclo-pentadiene and chloride ion are also produced in the case of Fe. The reactions do not proceed in non-polar solvents. At shorter wavelengths (λ > 280 nm) the principal product in all cases is a dimeric species which could not be isolated, but which spectral data suggest to correspond to displacement of one CO molecule by solvent from the dimers obtained at longer wavelengths; moreover i.r. and n.m.r. spectral profiles of the λ > 280 nm reaction indicate that the latter are essential intermediates in all three cases.Keywords
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