Radical reactions of diamine bis(phenolate) vanadium(iii) complexes. Solid state binding of O2 to form a vanadium(v) peroxo complex.

[VCl3(THF)3] reacted with the sodium salt of a tripodal diamine bisphenolate ligand precursor Na2L2 to give a paramagnetic d2 complex [V(L2)Cl] (2). The reaction of 2 with oxygen is strongly dependent on the experimental conditions, affording [VO(L2)Cl] (6) or [V(η2-O2)(L2)Cl] (7). The formation of 7 involves the direct addition of O2 to V(iii) in the solid state with oxidation to V(v) without significantly disturbing the structure of 2. DFT calculations showed that compound 7 is an intermediate in the formation of 6 from 2. The reaction involves the cleavage of the η1-O-O bond in a proposed dimeric species. The overall reaction of 2 moles of vanadium(iii), complex 2, and one mole of O2 to yield two moles of product 6 is a favourable process with ΔG298 = -38.3 kcal mol-1. 7 is the first non-oxido peroxidovanadium(v) complex obtained directly from the reaction of a crystal and the second example of a structurally characterized complex of that type. Reactions of V(L1)Cl (1) and V(L2)Cl (2) with one equivalent of the nitroxyl radical TEMPO in toluene also result in the formation of oxido V(v) complexes, VO(L1)Cl (5) and VO(L2)Cl (6). The reaction of VO(OiPr)3 with Na2L2 afforded [VO(L2)(OiPr)] (8) in high yield. A major isomer having the V[double bond, length as m-dash]O moiety in the equatorial plane was characterised by X-ray diffraction although solution NMR data showed the presence of a minor species with the oxido ligand trans to the tripodal nitrogen, as in 6. Complexes 6 and 8 are very active and selective sulfoxidation catalysts of thioanisole, but no enantiomeric excess was obtained.