Oxygen vanadium complexes

Photooxidafions are also iudustriaHy significant. A widely used treatment for removal of thiols from petroleum distillates is air iu the presence of sulfonated phthalocyanines (cobalt or vanadium complexes). Studies of this photoreaction (53) with the analogous ziuc phthalocyanine show a facile photooxidation of thiols, and the rate is enhanced further by cationic surfactants. For the perfume iudustry, rose oxide is produced iu low toimage quantifies by singlet oxygen oxidation of citroneUol (54). Rose bengal is the photosensitizer. 

Figure 6.5 Proposed structure for the vanadium complex prior to the oxygen transfer from peroxide to the allylic olefin.

The adsorption spectrum of aerosil containing admixture vanadium ions exhibits a maximum within the band 290 - 380 nm which was attributed by authors of [97] to the charge transfer transitions in oxygen-containing complexes of five valance vanadium = O -... 

To probe hydroperoxide reactivity in these systems we studied the reaction of tert-butyl hydroperoxide in the presence of [C5H5V(CO)4]. In contrast to the rhodium(I) and molybdenum complexes, [C5H5V-(CO)4] catalyzed the rapid decomposition of tert-butyl hydroperoxide to oxygen and tert-butyl alcohol in both toluene and TME (Table II). When reaction was done by adding the hydroperoxide rapidly to the vanadium complex in TME, no epoxide (I) was produced. However, when the TME solution of [C5H5V(CO)4] was treated with a small amount (2-3 times the molar quantity of vanadium complex) of tert-butyl hydroperoxide at room temperature, a species was formed in situ which could catalyze the epoxidation of TME. Subsequent addition of tert-butyl hydroperoxide gave I in 13% yield (Table II). This vanadium complex also could catalyze the epoxidation of the allylic alcohol (II) to give tert-butyl alcohol and IV (Reaction 14). Reaction 14 was nearly quantitative, and the reaction rate was considerably faster than with TME. 

Since the oxidative polymerization of diphenyl disulfide catalyzed by VO(acac)2 results in selective formation of thioether bonds without any oxygenated compounds such as sulfoxides and/or sulfones, it should be noted that H20 should be produced predominantly by the reduction of 02 catalyzed by the vanadium complex without the formation of partially reduced side products such as H202. 

If the OH group is not blocked at all but left free, and the epoxidation reagent is the vanadium complex VO(acac)2 combined with f-BuOOH, the syn epoxide is formed instead. The vanadyl group chelates reagent and alcohol and delivers the reactive oxygen atom to the same face of the alkene. 

The tetrameric vanadium complex contains also two sodium ions. Each is coordinated by two oxygen atoms of methanol molecules and by two oxygen atoms of different catechol molecules. Because of this coordination, oxygen atoms are Hj-bridging Na and V atoms. One of the three independent catechol molecules participates in the coordination of the vanadium atoms by one O only whereas the second atom is protonated and does not participate in the metal coordination. It is apparent that the complex... 

L-edge XAS features of two vanadium complexes with identical coordination environment bnt different oxidation number (-I-III and -fll), showing Lj (left) and Lj (cenbe). The weak bands to the right correspond to the excitation of oxygen (H. Nekola, Ph.D. thesis, Hamburg 2001 communicated by T. Fnnk and S. P. Cramer, Stanford Synchr. Rad. Lab., CA). ... 

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