Abstract

AbstractSynthesis and Characterization of Novel Five‐ and Six‐coordinate Manganese Complexes as Catechol Dioxygenase ModelsThe five‐ and six‐coordinate manganese complexes [Mn(tphhp)Cl2] {tphhp = N,N′‐bis(2‐pyridylmethyl)‐2‐(2‐pyridyl)hexahydropyrimidine} (1), [Mn(bpma)Cl](ClO4) {bpma = bis((2‐pyridylmethyl)((1‐methylbenzimidazol‐2‐yl)‐methyl)amine} (2) and [Mn(L)TCC] {HL = (1‐hydroxy‐4‐nitrobenzyl)((1‐methylimidazol‐2‐yl)methyl)(2‐pyridylmethyl)amine} (3) were synthesized and characterized by various techniques such as single crystal X‐ray structure analysis, mass spectrometry, IR and UV/vis spectroscopy, cyclic voltammetry, and elemental analysis. 1 and 2 crystallize in the monoclinic space group P21/n (No. 14) (1) and P21/c (No. 14) (2). The ligand and the chlorine ions provide the N3Cl2‐donorset in 1 and the N3Cl2‐donorset in 2, respectively. Compounds 1 and 2 show catalytic activity regarding the oxidation of 3,5‐di‐tertbutylcatechol to 3,5‐di‐tert‐butylchinon. To our knowledge, 1 and 2 are the first five‐coordinate manganese complexes that show catecholase activity. 3 crystallize in the orthorhombic space group P212121 (No. 19) and the ligand and tetrachlorocatechol (TCC) build the N3O3‐donorset in 3.

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