Theoretical rationalization for the equilibrium between (μ-η22-peroxido)CuIICuII and bis(μ-oxido)CuIIICuIII complexes: Perturbational effects from ligand frameworks

Tsukasa Abe, Yoshihito Shiota, Shinobu Itoh, Kazunari Yoshizawa

研究成果: Contribution to journalArticle査読


DFT calculations are carried out to investigate the geometric effects of the supporting ligands in the relative energies of the (μ-η22-peroxido)CuIICuII complex 1 and the bis(μ-oxido)CuIIICuIII complex 2. The N3-tridentate ligand bearing acyclic propane diamine framework La preferentially provided 1, whereas the N3-tridentate ligand with cyclic diamine framework such as 1,4-diazacycloheptane Lb gave 2 after the oxygenation of the corresponding CuI complexes as reported previously [S. Itoh, et al., Inorg. Chem., 2014, 53, 8786-8794]. Calculations at the B3LYP∗-D3 level of theory can reasonably explain the experimental results in relative energies, structures and harmonic frequencies of 1 and 2. Perturbational effects of the diamine chelates of La and Lb especially on the equilibrium of 1 and 2 are investigated in detail. In the range from 2.30 Å to 3.40 Å of the N-N distance in the diamine moiety, 1 is more stable than 2 by 8.4 kcal mol-1 at the distance of 3.40 Å. Calculated potential energies indicate that the decrease in the N-N distance is associated with a decrease in energy of 2, leading that 2 can be most stabilized at the N-N distance of 2.60 Å. Furthermore, molecular orbitals analyses are performed to explain that the energy gaps between the σ∗ orbital of the O-O bond and the dx2-y2 orbitals of the CuII ions of 1 get small as the diamine moiety is shrunk, leading to facilitate the O-O bond cleavage from 1 to 2.

ジャーナルDalton Transactions
出版ステータス出版済み - 5 28 2020

All Science Journal Classification (ASJC) codes

  • 無機化学


「Theoretical rationalization for the equilibrium between (μ-η<sup>2</sup>:η<sup>2</sup>-peroxido)Cu<sup>II</sup>Cu<sup>II</sup> and bis(μ-oxido)Cu<sup>III</sup>Cu<sup>III</sup> complexes: Perturbational effects from ligand frameworks」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。