Unimolecular Double Photoionization-Induced Processes in Iron Pentacarbonyl

[Image: see text] The dissociations of nascent Fe(CO)(5)(++) ions created by 40.81 eV photoionization of iron pentacarbonyl have been examined using threefold and fourfold electron–ion coincidence measurements. The energies and forms of the ions have been explored by high-level calculations, revealing several new structures. The most stable form of Fe(CO)(5)(++) has a quite different geometry from that of the neutral molecule. The dissociation pattern can be modeled as a sequence of CO evaporations followed by two-body charge separations. Each Fe(CO)(n)(++) (n = 1–4) dication is stable in a restricted energy range; as its internal energy increases, it first ejects a neutral CO, then loses CO(+) by charge separation at higher energy. In the initial stages, charge-retaining CO evaporations dominate over charge separation, but the latter become more competitive as the number of residual CO ligands decreases. At energies where ionization is mainly from the CO ligands, new Fe–C and C–C bonds are created by a mechanism which might be relevant to catalysis by Fe.