Manganese(IV)–hydroxo complex, C–H bond activation, Oxygen non-rebound mechanism
A high-valent manganese–hydroxo complex has been synthesized and characterized using various physicochemical methods such as UV–vis, ESI-MS, IRPD, and DFT calculations. Generally, manganese-oxygen adducts can activate C–H bond through an oxygen non-rebound mechanism where the rate of hydrogen atom transfer (HAT) depends on the strength of C–H bond. Herein, in the formation process of manganese–hydroxo complex, [MnIV(CHDAP–O)(OH)]2+, the C–H bond activation of the 2,6 position in cyclohexyl groups unusally proceeds via an oxygen rebound mechanism, in which HAT is identified as a rate determining step.
Table Of Contents
Contents Abstract i List of contents iii List of figures iv List of tables vi
II. Experimental section 2.1 Materials and Instrumentation 2 2.2 Synthesis 3 2.2.1 A deuterated CHDAP ligand 3 2.2.2 [MnII(CHDAP)(OTf)2] 5 2.2.3 [MnIV(CHDAP–O)(OH)]2+ 6 2.3 X-ray crystallography 6
III. Results and discussion
3.1 Preparation and Characterization of a Deuterated CHDAP Ligand 10 3.2 Synthesis and Characterization of a Manganese(II)-Starting Complex 12 3.3 Synthesis and Characterization of a Manganese(IV)–Hydroxo Complex 15 3.4 The Effect of the Deuterium Exchange in the 2,6 Position of Cyclohexyl Groups 20 3.5 Consideration 27