Simulation of UV/visible absorption spectra of (α‐diimine)nickel(II) catalysts by time‐dependent density functional theory

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The metal‐to‐ligand charge‐transfer excited states of (α‐diimine)‐NiII catalysts were simulated using time‐dependent density functional schemes for three reaction intermediates: the active site with a methyl group to mimic the growing alkyl chain, the corresponding π‐complex formed with an ethylene molecule, and the product where the propyl chain displays a γ‐agostic interaction. The simulations provide a basis for analyzing the experimental data in terms of charge‐transfer and enable one to assess the variations of the spectra upon modifications of the bidentate ligand. Moreover, the impact of the atomic basis set and exchange‐correlation functionals on the electronic absorption spectra was addressed in view of a more systematic use on new late transition metal catalysts.