Competition between One‐ and Two‐Electron Unimolecular Reactions of Late 3d‐Metal Complexes [(Me₃SiCH₂)<i>_n</i>M]^–(M = Fe, Co, Ni, and Cu; <i>n</i> = 2–4)

Although organometallic complexes of the late 3d elements are known to undergo both one-and two-electron reactions, their relative propensities to do so remain poorly understood. To gain direct insight into the competition between these different pathways, we have analyzed the unimolecular gas-phase reactivity of a series of well-defined model complexes [(Me₃SiCH₂)_nM]^- (M = Fe, Co, Ni, and Cu; n = 2-4). Applying a combination of tandem-mass spectrometry, quantum-chemical computations, and statistical rate-theory calculations, we find several different fragmentation reactions, among which the homolytic cleavage of metal-carbon bonds and radical dissociations are particularly prominent. In all cases, these one-electron reactions are entropically favored. For the ferrate and cobaltate complexes, they are also energetically preferred, which explains their predominance in the corresponding fragmentation experiments. For [(Me₃SiCH₂)₄Ni]^- and, even more so, for [(Me₃SiCH₂)₄Cu]^-, a concerted reductive elimination as a prototypical two-electron reaction is energetically more favorable and gains in importance. [(Me₃SiCH₂)₃Ni]^- is special in that it has two nearly degenerate spin states, both of which react in different ways. A simple thermochemical analysis shows that the relative order of the first and second bond-dissociation energies is of key importance in controlling the competition between radical dissociations and concerted reductive eliminations.