4 years ago

Detection of an unusual intermediate in the photolysis of an iron tricarbonyl complex

Detection of an unusual intermediate in the photolysis of an iron tricarbonyl complex
UV photoexcitation of trans-(η4-BDA)Fe(CO)3 (1) in alkane solvent generated a short-lived isomeric species whose identity was confirmed by infrared spectroscopy and supported by DFT calculations. This intermediate (2) exhibits an unusual ɳ2 coordination of the benzyl group to a vacant site on the iron center and is computed to be 7.8 kcal/mol less stable than 1. While thermal substitution of the BDA ligand from 1 by phosphites was found to be very slow at room temperature, photolysis of 1 in the presence of P(OEt)3 results in BDA displacement from 2 within seconds. Intermediate 2 may be of relevance in the previously reported photocatalyic dehydrogenation of formic acid by 1.

Publisher URL: www.sciencedirect.com/science

DOI: S0022328X17305508

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