TY - JOUR
T1 - Theoretical rationalization for the equilibrium between (μ-η2:η2-peroxido)CuIICuII and bis(μ-oxido)CuIIICuIII complexes
T2 - Perturbational effects from ligand frameworks
AU - Abe, Tsukasa
AU - Shiota, Yoshihito
AU - Itoh, Shinobu
AU - Yoshizawa, Kazunari
N1 - Funding Information:
K. Y. acknowledges KAKENHI Grant numbers JP15K13710 and JP17H03117 from Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT), the MEXT Projects of “Integrated Research Consortium on Chemical Sciences”, “Cooperative Research Program of Network Joint Research Center for Materials and Devices”, “Elements Strategy Initiative to Form Core Research Center”, JST-CREST JPMJCR15P5 and JST-Mirai JPMJMI18A2. The computational study was mainly carried out using the computer facilities at Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2020 The Royal Society of Chemistry.
PY - 2020/5/28
Y1 - 2020/5/28
N2 - DFT calculations are carried out to investigate the geometric effects of the supporting ligands in the relative energies of the (μ-η2:η2-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.
AB - DFT calculations are carried out to investigate the geometric effects of the supporting ligands in the relative energies of the (μ-η2:η2-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.
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U2 - 10.1039/d0dt01001d
DO - 10.1039/d0dt01001d
M3 - Article
C2 - 32368776
AN - SCOPUS:85085536507
VL - 49
SP - 6710
EP - 6717
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 20
ER -