One pot synthesis of two cobalt(iii) Schiff base complexes with chelating pyridyltetrazolate and exploration of their bio-relevant catalytic activities.

Two new cobalt(iii) tetrazolato complexes [Co(L 1 )(PTZ)(N 3 )] (1) and [Co(L 2 )(PTZ)(N 3 )] (2) {where H 2 L 1 = 2((3-(methylamino)propylimino)methyl)-6-methoxyphenol, H 2 L 2 = 2((3-(dimethylamino)propylimino)methyl)-6-ethoxyphenol and HPTZ = 5-(2-pyridyl)tetrazole}, have been synthesized via in situ 1,3-dipolar cycloaddition reaction of 2-cyanopyridine and sodium azide in the presence of cobalt(ii) nitrate hexahydrate and respective Schiff bases in the open atmosphere. The structures of both complexes have been confirmed by single crystal X-ray diffraction studies. Features of noncovalent interactions in the solid state of both complexes have been studied by means of DFT and MEP calculations and characterized using Bader's theory of "atoms in molecules" (AIM). These complexes act as biomimetic catalysts promoting the aerobic oxidation of 3,5-di- tert -butylcatechol (3,5-DTBC) to the corresponding o -benzoquinone at room temperature. The reaction follows Michaelis-Menten enzymatic reaction kinetics with turnover numbers of ∼0.030 s -1 in an acetonitrile-methanol (2 : 1) mixture. Both complexes are also reactive towards aerobic oxidation of o -aminophenol in acetonitrile-methanol (2 : 1) with turnover numbers ∼0.095 s -1 .