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A Structurally Analogous Series of Mn(II), Fe(II), and Co(II) Complexes Which Exhibit Three Distinct Reactivities
Vishal Yadav1, Lyupeng Wen1, Sudha Yadav1
1Department of Chemistry, the Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland21218, United States.
None:
The synthesis and characterization of a series of nonheme Fe(II), Mn(II), and Co(II) complexes, MII(BNPAPh2O)(Cl) (M = Fe, Mn, Co), are reported. These complexes were characterized using single-crystal X-ray crystallography, 1H NMR spectroscopy, and ATR-FTIR spectroscopy to establish their structural and electronic properties. Their reactivity with dioxygen revealed distinct metal-dependent pathways. The Mn(II) complex undergoes ligand-based C-N bond cleavage, forming a pentanuclear cluster, whereas the Fe(II) complex reacts with O2 to generate a well-defined FeIII(BNPAPh2O)(OH)(Cl) species, relevant to the rebound intermediate in nonheme iron halogenases. In contrast, the Co(II) complex exhibits no detectable reactivity toward O2. These differences illuminate the intrinsic metal-dependent factors that govern O2 activation and underscore the central role of metal identity in tuning reactivity and selectivity in bioinorganic oxidation chemistry.
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