Synthesis, Characterization and Reactivity of a Mn(III)-hydroxido Complex As a Biomimetic Model for Lipoxygenase

Overview

Journal J Inorg Biochem

Specialty Biochemistry

Date 2024 Jul 10

PMID 38986289

Authors

Phan N Phu

Suman K Barman

Joseph W Ziller

Michael P Hendrich

A S Borovik

Affiliations

Soon will be listed here.

Abstract

Manganese hydroxido (Mn-OH) complexes supported by a tripodal N,N',N″-[nitrilotris(ethane-2,1-diyl)]tris(P,P-diphenylphosphinic amido) ([poat]) ligand have been synthesized and characterized by spectroscopic techniques including UV-vis and electron paramagnetic resonance (EPR) spectroscopies. X-ray diffraction (XRD) methods were used to confirm the solid-state molecular structures of {Na[Mnpoat(OH)]} and {Na[Mnpoat(OH)]} as clusters that are linked by the electrostatic interactions between the sodium counterions and the oxygen atom of the ligated hydroxido unit and the phosphinic (P=O) amide groups of [poat]. Both clusters feature two independent monoanionic fragments in which each contains a trigonal bipyramidal Mn center that is comprised of three equatorial deprotonated amide nitrogen atoms, an apical tertiary amine, and an axial hydroxido ligand. XRD analyses of {Na[Mnpoat(OH)]} also showed an intramolecular hydrogen bonding interaction between the Mn-OH unit and P=O group of [poat]. Crystalline {Na[Mnpoat(OH)]} remains as clusters with Na---O interactions in solution and is unreactive toward external substrates. However, conductivity studies indicated that [Mnpoat(OH)] generated in situ is monomeric and reactivity studies found that it is capable of cleaving C-H bonds, illustrating the importance of solution-phase speciation and its direct effect on chemical reactivity. Synopsis: Manganese-hydroxido complexes were synthesized to study the influence of H-bonds in the secondary coordination sphere and their effects on the oxidative cleavage of substrates containing C-H bonds.

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