Journal
INORGANIC CHEMISTRY
Volume 53, Issue 1, Pages 645-652Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic402831f
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Funding
- NRF/MEST of Korea through the CRI [2-2012-1794-001-1]
- NRF/MEST of Korea through GRL [2010-00353]
- Basic Research Program [2010-0002558]
- RD programs [13-BD-0403, 2013K2A2A4000610]
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The mechanism of the C-H bond activation of hydrocarbons by a nonheme chromium(IV) oxo complex bearing an N-methylated tetraazamacrocyclic cyclam (TMC) ligand, [Cr-IV(O)(TMC)(Cl)](+) (2), has been investigated experimentally and theoretically. In experimental studies, reaction rates of 2 with substrates having weak C-H bonds were found to depend on the concentration and bond dissociation energies of the substrates. A large kinetic isotope effect value of 60 was determined in the oxidation of dihydroanthracene (DHA) and deuterated DHA by 2. These results led us to propose that the C-H bond activation reaction occurs via a H-atom abstraction mechanism, in which H-atom abstraction of substrates by 2 is the rate-determining step. In addition, formation of a chromium(III) hydroxo complex, [Cr-III(OH)(TMC)(Cl)](+) (3), was observed as a decomposed product of 2 in the C-H bond activation reaction. The (CrOH)-O-III product was characterized unambiguously with various spectroscopic methods and X-ray crystallography. Density functional theory (DFT) calculations support the experimental observations that the C-H bond activation by 2 does not occur via the conventional H-atom-abstraction/oxygen-rebound mechanism and that 3 is the product formed in this C-H bond activation reaction. DFT calculations also propose that 2 may have some (CrO center dot-)-O-III character. The oxidizing power of 2 was then compared with that of a chromium(III) superoxo complex bearing the identical TMC ligand, [Cr-III(O-2)(TMC)(Cl)](+) (1), in the C-H bond activation reaction. By performing reactions of 1 and 2 with substrates under identical conditions, we were able to demonstrate that the reactivity of 2 is slightly greater than that of I. DFT calculations again support this experimental observation, showing that the rate-limiting barrier for the reaction with 2 is slightly lower than that of 1.
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