Intramolecular ligand hydroxylation: Mechanistic high-pressure studies on the reaction of a dinuclear copper(I) complex with dioxygen

We provide a mechanistic study of a monooxygenase model system and detail l ow-temperature stopped-flow kinetics studies in acetone as solvent, employi ng both the use of rapid-scanning diode-array observation and variable high -pressure (20-100 MPa) techniques. The dicopper(I) complex employed is [Cu- 2(H-XYL-H)](2+) (1), with the H-XYL-H ligand wherein a m-xylyl group links two bis[2-(2-pyridyl)ethyl]amine units. This reacts with O-2 reversibly (k( 1)/k(-1)) giving a peroxo-dicopper(II) intermediate [Cu-2(H-XYL-H)(O-2)](2) (2), which thereupon irreversibly (k(2)) reacts by oxygen atom insertion (i.e., hydroxylation) of the xylyl group, producing [Cu-2(H-XYL-O-)(OH)](2) (3). Activation parameters are as follows: k(1), Delta H-double dagger = 2.1 +/- 0.7 kJ/mol, Delta S-double dagger = -174 +/- 3 J/(K mel); k(-1), De lta H-double dagger = 80.3 +/- 0.8 kJ/mol, Delta S-double dagger = 77 +/- 3 J/(K mel); k(2), Delta H-double dagger = 58.2 +/- 0.2 kJ/mol, Delta S-doub le dagger = -5.8 +/- 0.9 J/(K mel). These values are similar to values obta ined in a previous study in dichloromethane. At low temperatures and higher concentrations, the situation in acetone is complicated by a pre-equilibri um of 1 to an isomer form. The present study provides the first determinati on of activation volumes for individual steps in copper monooxygenase react ions. The data and analysis provide that Delta V-double dagger(k(1)) = -15 +/- 2.5 cm(3)/mol and Delta V-double dagger(k(-1)) +4.4 +/- 0.5 cm(3)/mol f or formation and dissociation of 2, respectively, while Delta V-double dagg er(k(2)) = -4.1 +/- 0.7 cm(3)/mol; a volume profile for the overall reactio n has been constructed. The significance of the findings in the present stu dy is described, and the results are compared to those for other systems.