1312908-99-8Relevant academic research and scientific papers
Functional mimics of catechol oxidase by mononuclear copper complexes of sterically demanding [NNO] ligands
Panda, Manas K.,Shaikh, Mobin M.,Butcher, Ray J.,Ghosh, Prasenjit
, p. 145 - 151 (2011)
Several mononuclear copper complexes 1(a-b) and 2(a-b) supported over sterically demanding [NNO] ligands namely, N-(aryl)-2-[(pyridin-2-ylmethyl) amino]acetamide [aryl = 2,6-diethylphenyl (1) and mesityl (2)], exhibit catecholase-like activity in performing the aerial oxidation of 3,5-di-t-butylcatehol (3,5-DTBC) to 3,5-di-t-butyl-catequinone (3,5-DTBQ) under ambient conditions. The 1(a-b) and 2(a-b) complexes were directly synthesized from the reaction of the respective ligands 1-2 with CuX2· nH2O (X = Cl, NO3, n = 2, 3) in 55-85% yield. Mechanistic insights on the catalytic cycle as obtained by density functional theory studies for a representative complex 1a suggest that an intramolecular hydrogen transfer, from a catechol-OH moiety to a copper bound superoxo moiety, form the rate-determining step of the oxidation process, displaying an activation barrier of 18.3 kcal/mol (ΔG?) [6.9 kcal/mol in Δ(PE + ZPE)? scale].
