Subtle Structural Changes in (Cu^IIL)₂Mn^II Complexes To Induce Heterometallic Cooperative Catalytic Oxidase Activities on Phenolic Substrates (H₂L = Salen Type Unsymmetrical Schiff Base)

Abstract

A new Cu(II) complex of an asymmetrically dicondensed Schiff base (HL = N-(2-hydroxyacetophenylidene)-N'-salicylidene-1,3-propanediamine) derived from 1,3-propanediamine, salicylaldehyde, and o-hydroxyacetophenone has been synthesized. Using this complex, [CuL] (1), as a metalloligand, two new trinuclear Cu-Mn complexes, [(CuL)Mn(N)(HO)](ClO)·HO (2) and [(CuL)Mn(NCS)] (3), have been prepared. Single-crystal structural analyses reveal that complexes 2 and 3 both have the same bent trinuclear {(CuL)Mn} structural unit in which two terminal bidentate square-planar (CuL) units are chelated to the central octahedral Mn(II) ion. This structural similarity is also evident from the variable-temperature magnetic susceptibility measurements, which suggest that compounds 2 and 3 are both antiferromagnetically coupled with comparable exchange coupling constants (-21.8 and -22.3 cm, respectively). The only difference between 2 and 3 lies in the coordination around the central Mn(II) ion; in 3, two SCN groups are coordinated to the Mn(II), leaving a neutral complex, but in 2, one N group and one HO molecule are coordinated to give a positively charged species. The presence of such a labile HO coligand makes 2 catalytically active in mimicking two well-known polynuclear copper proteins, catecholase and phenoxazinone synthase. The turnover numbers (k) for the aerial oxidation of 3,5-di-tert-butylcatechol and o-aminophenol are 1118 and 6581 h, respectively, values which reflect the facility of the heterometallic catalyst in terms of both efficiency and catalytic promiscuity for aerial dioxygen activation. The mechanisms of these biomimetic oxidase reactions are proposed for the first time involving any heterometallic catalyst on the basis of mass spectral analysis, EPR spectroscopy, and cyclic voltammetry. The evidence of the intermediates indicates possible heterometallic cooperative activity where the substrates bind to a Mn(II) center and Cu(II) plays the role of an electron carrier for transformation of the phenolic substrates to their respective products with the reduction of aerial dioxygen.

Ligand‐Centered Radical Activity by a Zinc‐Schiff‐Base Complex towards Catechol Oxidation

“…Though this Schiff base ligand ( L ) actually behaves as a polydentate ligand but all the donor centres are not employed in the formation of Zn(II) complex. Previously it was seen that this ligand acted as an important backbone for making hetero‐metallic clusters (3d–4f) which led to important magnetic properties ,. In this present case, this particular ligand actually displays selectivity towards Zn(II) ion and for this reason it is observed that methoxy‐O (O3 & O4) and alkoxy‐O (O6) remains unemployed in the structural building,…”

B12H122–‐Based Metal (Cu2+, Ni2+, Zn2+) Complexes as Hypergolic Fuels with Superior Hypergolicity

“…Complex 1 consists of a square‐planar coordinated structure around a central metal ion [Cu 2+ ] and a completely symmetric decahedron of boron. In the symmetric unit, four coordinated alkylimidazole N atoms constituted the basal plane around Cu 2+ . There are fewer contacts between the C atoms and the N atoms in the different ligands.…”

Syntheses and Crystal Structures of Mn(II), Ni(II) and Cu(II) Coordination Compounds Assembled by Maleato and Dimethyl-2,2′-bipyridines

“…6). Relatively few coordination complexes, or polymers, have been reported showing this type of Cu 2 O 2 rhombic cluster [29][30][31][32][33][34]. The Cu centers are fivecoordinated and surrounded by three oxygen atoms from two mal ligands and two nitrogen atoms from one 4dmb ligand.…”