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A DFT study on the C-H oxidation reactivity of Fe(iv)-oxo species with N4/N5 ligands derived from l-proline
Jin Lin1,2, Qiangsheng Sun1, Wei Sun1
1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences Lanzhou 730000 P. R. China wsun@licp.cas.cn.
Abstract:
The hydroxylation of hexane by two FeIVO complexes bearing a pentadentate ligand (N5, Pro3Py) and a tetradentate ligand (N4, Pro2PyBn) derived from l-proline was studied by DFT calculations. Theoretical results predict that both FeIVO complexes hold triplet ground states. The hydrogen atom abstraction (HAA) processes by both FeIVO species proceed through a two-state reactivity, thus indicating that HAA occurs via a low-barrier quintet surface. Beyond the conventional rebound step, the dissociation path is also calculated and is found to potentially occur after HAA.
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