Crystal structure, magnetic and catalytic oxidation properties of manganese(iii) tetrakis(ethoxycarbonyl)porphyrin

Abstract

5,10,15,20-tetrakis(ethoxycarbonyl)porphyrin manganese(iii) chloride (MnIIITECPCl) existed as a Mn–O coordinated dimer. MnIIITECPCl gave high yield in oxidation of styrene by using TBHP or PhIO oxidant and was found recyclable.

Switchable Aromaticity in an Isostructural Mn Phthalocyanine Series Isolated in Five Separate Redox States

“…Single crystals suitable for XRD studies were grown by layering benzene over a saturated fluorobenzene solution and confirmed the structure as the Mn­(III) species, EtO PcMnCl ( 1 ) (Figure S27). Bond metrics are similar to other Mn­(III)Cl macrocyclic species, such as a similar porphyrin derivative . The high-spin, S = 2 state at Mn was confirmed by solution magnetic moment determination using the Evans method, and resulted in paramagnetically broadened resonances in the 1 H NMR spectrum.…”

“…The average C α –C β bond length for 2 + and 2 – do not vary significantly from the values of 2 (Figure S33B). Additionally, the MN bond length in both 2 + (1.526(5) Å) and 2 – (1.497(8) Å) relative to 2 (1.555(9) Å) seem to suggest little electronic participation of the metal or apical nitrogen toward these events, corroborating the solution-state spectra that suggest a highly delocalized radical residing on the ring, a common state for mono-oxidized and monoreduced macrocyclic systems. ,,− …”

“…Bond metrics are similar to other Mn(III)Cl macrocyclic species, such as a similar porphyrin derivative. 35 The high-spin, S = 2 state at Mn was confirmed by solution magnetic moment determination using the Evans method, 36 and resulted in paramagnetically broadened resonances in the 1 H NMR spectrum.…”

Mg–Al layered double hydroxide intercalated with manganese(III) 5,10,15,20‐tetrakis(4‐benzoate)porphyrinacetate as a highly reusable catalyst for epoxidation

“…Over the last three decades, many efficient catalytic methodologies have been developed for the synthesis of structurally diverse epoxides . Manganese porphyrins have long been known as valuable biomimetic catalysts for oxidation of both unsaturated and saturated hydrocarbons because of their high selectivity and efficiency; in particular, epoxidation of olefins with manganese porphyrins has been extensively studied . Homogeneous catalytic media suffer from lack of recyclability, and to overcome such a problem heterogenization of such systems would be of help …”

Water-soluble Manganese and Iron Mesotetrakis(carboxyl)porphyrin: DNA Binding, Oxidative Cleavage, and Cytotoxic Activities

“…Previous studies have confirmed that anionic porphyrins have better membrane permeability than cationic ones [ 35 , 36 , 37 ], which may explain their higher biological activity. In order to extend the biological application scope of anionic porphyrins, two new water-soluble anionic manganese (III) and iron (III) meso -tetrakis (carboxyl) porphyrin were prepared by hydrolysis of their corresponding 5,10,15,20-tetrakis (ethoxycarbonyl) porphyrin metal complexes [ 38 , 39 ] ( Figure 1 ). The DNA binding and nuclease activity of the anionic complexes were examined by various spectral, viscosity and gel electrophoresis measurements.…”