Revealing the Structure of Transition Metal Complexes of Formaldoxime

Aerobic reactions of iron(III), nickel(II), and manganese(II) chlorides with formaldoxime cyclotrimer (tfoH₃) and 1,4,7-triazacyclononane (tacn) produce indefinitely stable complexes of general formula [M(tacn)(tfo)]Cl. Although the formation of formaldoxime complexes has been known since the end of 19th century and applied in spectrophotometric determination of d-metals (formaldoxime method), the structure of these coordination compounds remained elusive until now. According to the X-ray analysis, [M(tacn)(tfo)]⁺ cation has a distorted adamantane-like structure with the metal ion being coordinated by three oxygen atoms of deprotonated tfoH₃ ligand. The metal has a formal +4 oxidation state, which is atypical for organic complexes of iron and nickel. Electronic structure of [M(tacn)(tfo)]⁺ cations was studied by XPS, NMR, cyclic (CV) and differential pulse (DPV) voltammetries, Mössbauer spectroscopy, and DFT calculations. Unusual stabilization of high-valent metal ion by tfo^3- ligand was explained by the donation of electron density from the nitrogen atom to the antibonding orbital of the metal-oxygen bond via hyperconjugation as confirmed by the NBO analysis. All complexes [M(tacn)(tfo)]Cl exhibited high catalytic activity in the aerobic dehydrogenative dimerization of p-thiocresol under ambient conditions.