Utilizing tetraphenylporphyrin (TPP), tetratolylporphyrin (TTP), tetramesitylporphyrin (TMP), and tetra- p -chlorophenylporphyrin (T p ClPP) as ligands, several five-coordinate high-spin p -toluenethiolate Manganese(II) complexes are isolated and studied by UV-vis, single-crystal X-ray and EPR spectroscopies. The crystal structures show noteworthy features including flexible axial p -toluenethiolate ligands and intramolecular C−H ⋅ ⋅ ⋅ π and π - π interactions between ligands and porphyrin planes. All four products are further studied by X-band EPR on both solid and solution states at 4 K which confirmed the S = 2/5 high-spin states. Temperature-dependent EPR and measurements with different equivalents of ligands are also reported for comparison. The work provides new references for the study of the active center of P450s and the biochemical reaction between cysteine residues and heme.
Molybdenum nitride, because of the strong metal-support interaction between nitrogen and the metal, exhibits activity superior to that of bare metals, demonstrating its effectiveness as a co-catalyst to address the slow kinetics of the iron reduction in the Fenton process. Here, we introduced Mo 2 N as a co-catalyst to accelerate the cycles of Fe 3+ /Fe 2+ within a Fenton-like system consisting of Fe 3+ and H 2 O 2 , thereby enhancing the activation of hydrogen peroxide to generate reactive oxygen species (ROS). The system demonstrates excellent recyclability and stability. XPS spectroscopic analyses reveal that Mo(III) and Mo(IV) species on the Mo 2 N surface are capable of reducing free Fe(III), while FTIR analyses show nitrogen (N) and nitrogen oxide (NO x ) facilitate the adsorption and coordination of iron. Both homogeneous and heterogeneous reduced iron species are active in the activation of H 2 O 2 . EPR spectroscopy further confirms that the primary ROS generated are hydroxyl radicals (·OH) and superoxide anions (·O 2 − ). This study not only underscores the feasibility of Mo 2 N-based Fenton-like systems but also provides a new strategy for promoting the practical application of Fenton chemistry. Graphical
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