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End-on versus side-on coordination of dioxygen model ab initio calculations for the adducts of Co(acacen)

Abstract

From ab initio calculations, the ground state electronic configuration is found for the three possible structures (linear, bent or perpendicular) of the cobalt-dioxygen unit in the adducts Co(acacen) LO2(L=none, H2O, CN, CO). The bent structure is energetically the most favourable, being slightly more stable than the linear one (by 4–26 kcal/mole depending on the fifth ligand L) but much more stable than the perpendicular one (by 46–82 kcal/mole). These results are rationalized in terms of the main metal-ligand interactions, with the bent structure stabilized by a 3d z 2-1π g /a interaction and the perpendicular structure destabilized by a four-electron destabilizing interaction 3d xz -1π g /a .

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Rohmer, M., Dedieu, A. & Veillard, A. End-on versus side-on coordination of dioxygen model ab initio calculations for the adducts of Co(acacen). Theoret. Chim. Acta 39, 189–195 (1975). https://doi.org/10.1007/BF00550321

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Key words

  • Co(acacen), adducts of ∼
  • Dioxygen, coordination of ∼