Abstract
With the aim of modeling reactive moieties and relevant intermediates on the surfaces of vanadium oxide based catalysts during oxygenation/dehydrogenation of organic substrates, mono‐ and dinuclear vanadium oxo complexes of doubly deprotonated p‐tert‐butylated tetrathiacalix[4]arene (H~4~TC) have been synthesized and characterized: PPh~4~[(H~2~TC)VOCl~2~] (1) and (PPh~4~)~2~[{(H~2~TC)V(O)(μ‐O)}~2~] (2). According to the NMR spectra of the dissolved complexes they both retain the structures adopted in the crystalline state, as revealed by single‐crystal X‐ray crystallography. Compounds 1 and 2 were tested as catalysts for the oxidation of alcohols with O~2~ at 80 °C. Both 1 and 2 efficiently catalyze the oxidation of benzyl alcohol, crotyl alcohol, 1‐phenyl‐1‐propanol, and fluorenol, and in most cases dinuclear complex 2 is more active than mononuclear complex 1. Moreover, the two thiacalixarene complexes 1 and 2 are in many instances more active than oxovanadium(V) complexes containing “classical” calixarene ligands tested previously. Complexes 1 and 2 also show significant activity in the oxidation of dihydroanthracene. Further investigations led to the conclusion that 1 acts as precatalyst that is converted to the active species PPh~4~[(TC)VO] (3) at 80 °C by double intramolecular HCl elimination. For complex 2, the results of mechanistic investigations indicated that the oxidation chemistry takes place at the bridging oxo ligands and that the two vanadium centers cooperate during the process. The intermediate (PPh~4~)~2~[{H~2~TCV(O)}~2~(μ‐OH)(μ‐OC~13~H~9~)] (4) was isolated and characterized, also with respect to its reactivity, and the results afforded a mechanistic proposal for a reasonable catalytic cycle. The implications which these findings gathered in solution may have for oxidation mechanisms on the surfaces of V‐based heterogeneous catalysts are discussed.