We regard dissociation processes induced by femtosecond excitation of iron pentacarbonyl. In common time-resolved ionization experiments, the total ion yield is detected as a function of the delay time between pump- and probe-pulse. If several ionic fragments are produced, these measurements cannot distinguish between charged molecules produced via ionization of neutral molecules or fragmentation of larger molecular ions. We show that time-resolved photoelectron spectroscopy does not suffer from this deficiency and thus provides a unique tool to investigate neutral fragmentation processes.