X-Band Electron Paramagnetic Resonance Comparison of Mononuclear MnIV-oxo and MnIV-hydroxo Complexes and Quantum Chemical Investigation of MnIV Zero-Field Splitting
作者： Domenick F. Leto , Allyssa A. Massie , Hannah E. Colmer , Timothy A. Jackson
DOI: 10.1021/ACS.INORGCHEM.5B02309
关键词: Analytical chemistry 、 Electron paramagnetic resonance 、 Redox 、 Hyperfine structure 、 Zero field splitting 、 Crystallography 、 Proton 、 Manganese 、 Electron 、 Spectroscopy 、 Chemistry
摘要: X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear MnIV complexes [MnIV(OH)2(Me2EBC)]2+ and [MnIV(O)(OH)(Me2EBC)]+. These compounds are known effect C–H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing MnIV-hydroxo versus MnIV-oxo motifs, as they differ only proton. Simulations 5 K EPR data, along with analysis variable-temperature signal intensities, allowed estimation zero-field splitting (ZFS) 55Mn hyperfine parameters both complexes. From this analysis, it concluded that complex [MnIV(O)(OH)(Me2EBC)]+ has axial ZFS parameter D (D = +1.2(0.4) cm–1) rhombicity (E/D 0.22(1)) perturbed relative analogue (|D| 0.75(0.25) cm–1; E/D 0.15(2)), although have similar values (a 7.7 7.5 mT, respectively). The [MnIV(O...
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