Theoretical study on reaction between bis(μ-peroxo)dicopper(2)complex and phenol by “paired interacting orbitals (PIO)” analysis

• Published in: Journal of molecular catalysis. A, Chemical Vol. 241; no. 1; pp. 199 - 204
• Main Authors: Shiga, Akinobu, Kurusu, Yasuhiko
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.11.2005; Elsevier
• Subjects: (μ-Peroxo)dicopper complex; Catalysis; Chemistry; Exact sciences and technology; General and physical chemistry; Paired interacting orbitals (PIO) analysis; Phenol; Phenoxodicopper complex; Reaction mechanism; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Reaction mechanism; Phenol; (μ-Peroxo)dicopper complex; Paired interacting orbitals (PIO) analysis; Phenoxodicopper complex; Transition element complexes; Theoretical study; Alcohol; Copper complex; Peroxo complex; Phenols; Benzenic compound; Orbital
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2005.06.065

A reaction between μ-η 2:η 2-dibridging peroxodicopper complex of bis[3-(2-hydroxybenzylideneamino)phenyl]sulfone and phenol are investigated by using paired interacting orbitals (PIO) analysis proposed by Fujimoto et al. By observing the contour maps and overlap populations of main PIOs, it is clearly suggested that formation of mono-phenoxo complex is easy, however di-phenoxo complex formation is difficult. ▪ The reaction between μ-η 2:η 2-dibridging peroxodicopper complex of bis[3-(2-hydroxybenzylideneamino)phenyl]sulfone and phenol are investigated by performing paired interacting orbitals (PIO) analysis proposed by Fujimoto et al. Perusal of the contour maps and overlap populations of main PIOs suggested that formation of mono-phenoxo complex is easy; however di-phenoxo complex formation is difficult because of the non-flexibility of the SO 2-bridged ligand. This result supplies the reason why poly (phenylene oxide) was not formed in our system.