Molecular and electronic structure of octahedral o-aminophenolato and o-iminobenzosemiquinonato complexes of V(V), Cr(III), Fe(III), and Co(III). Experimental determination of oxidation levels of ligands and metal ions

The coordination chemistry of the ligands 2-anilino-4,6-di-tert-butylphenol, HL(AP)], and N,N"'-bis2-(4,6-di-tert-butylphenol]diethylenetriamine, H(2)(L(AP))N(L(AP))], has been studied with the first-row transition metal ions V, Cr, Fe, and Co. The ligands are noninnocent in the sense that the aminophenolato parts, L(AP)](-) and L(AP)-H](2)(-), can be readily oxidized to their o-iminobenzosemiquinonato, L(ISQ)](-), and o-iminobenzoquinone, L(ISB)], forms. The following neutral octahedral complexes have been isolated as crystalline materials, and their crystal structures have been determined by X-ray crystallography at 100 K: Cr(III)(L(ISQ))(3)] (1), Fe(III)(L(ISQ))(3)] (2), Co(III)(L(ISQ))(3)] (3), V(V)(L(ISQ))(L(AP)-H)(2)] (4), V(V)(L(AP)-H)(2)(L(AP))] (5), and V(V)O(L(AP))N(L(AP)-H)]] (6). From variable-temperature magnetic susceptibility measurements and X-band EPR spectroscopy it has been established that they possess the ground states: 1, S = 0; 2, S = 1; 3, S = (3)/(2); 4, S = (1)/(2); 5, S = 0; 6, S = 0. The o-iminobenzosemiquinonato radicals (S(rad) = (1)/(2)) couple strongly intramolecularly antiferromagnetically to singly occupied orbitals of the t(2g) subshell at the respective metal ion but ferromagnetically to each other in 3 containing a Co(III) ion with a filled t(2g)(6) subshell. It is demonstrated that the oxidation level of the ligands and metal ions can be unequivocally determined by high-quality X-ray crystallography in conjunction with EPR, UV-vis, and M?ssbauer spectroscopies. The spectro- and electrochemistry of these complexes have also been studied in detail. Metal- and ligand-based redox chemistry has been observed. The molecular and electronic structures are compared with those of their o-semiquinonato analogues.