Aliphatic and Aromatic C-H Bond Oxidation by High-Valent Manganese(IV)-Hydroxo Species.

The strong C-H bond activation of hydrocarbons is a difficult reaction in environmental and biological chemistry. Herein, a high-valent manganese(IV)-hydroxo complex, [Mn(CHDAP-O)(OH)] (), was synthesized and characterized by various physicochemical measurements, such as ultraviolet-visible (UV-vis), electrospray ionization-mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR), and helium-tagging infrared photodissociation (IRPD) methods. The one-electron reduction potential () of was determined to be 0.93 V vs SCE by redox titration. is formed via a transient green species assigned to a manganese(IV)-bis(hydroxo) complex, [Mn(CHDAP)(OH)] (), which performs intramolecular aliphatic C-H bond activation. The kinetic isotope effect (KIE) value of 4.8 in the intramolecular oxidation was observed, which indicates that the C-H bond activation occurs via rate-determining hydrogen atom abstraction. Further, complex can activate the C-H bonds of aromatic compounds, anthracene and its derivatives, under mild conditions. The KIE value of 1.0 was obtained in the oxidation of anthracene. The rate constant () of electron transfer (ET) from ,'-dimethylaniline derivatives to is fitted by Marcus theory of electron transfer to afford the reorganization energy of ET ( = 1.59 eV). The driving force dependence of log for oxidation of anthracene derivatives by is well evaluated by Marcus theory of electron transfer. Detailed kinetic studies, including the KIE value and Marcus theory of outer-sphere electron transfer, imply that the mechanism of aromatic C-H bond hydroxylation by proceeds via the rate-determining electron-transfer pathway.