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We report measurements of the primary photochemical fragmentation of iron pentacarbonyl into the species Fe(CO)5-n(1⩽n⩽4) resulting from one-photon absorption at 352, 248, and 193 nm. We have observed a high degree of fragmentation, with increasing fragmentation at shorter wavelengths. We believe that the fragmentation results from sequential loss of carbon monoxide with a high degree of retention of internal excitation in the resulting Fe(CO)5-n fragments. A surprisal analysis shows that the fragmentation pattern is highly nonstatistical. The variation in fragmentation with input energy is consistent with a statistical model in which the vibrational space is restricted to a single vibrational degree of freedom. Alternatively, dissociation may proceed through a sequence of electronically excited fragments. Both pictures are consistent with a plausible molecular orbital argument.

Die Reaktion des Allyl‐Fe‐Komplexes (I) mit kationischen Elektrophilen führt in.