Vanadium complex compounds others from

Epoxidation of allylic alcohols with peracids or hydroperoxide such as f-BuOaH in the presence of a transition metal catalyst is a useful procedure for the synthesis of epoxides, particularly stereoselective synthesis [587-590]. As the transition metal catalyst, molybdenum and vanadium complexes are well studied and, accordingly, are the most popular [587-590], (Achiral) titanium compounds are also known to effect this transformation, and result in stereoselectivity different from that of the aforementioned Mo- and V-derived catalysts. The stereochemistry of epoxidation by these methods has been compared for representative examples, including simple [591] and more complex trcMs-disubstituted, rrans-trisubstituted, and cis-trisubstituted allyl alcohols (Eqs (253) [592], (254) [592-594], and (255) [593]). In particular the epoxidation of trisubstituted allyl alcohols shown in Eqs (254) and (255) highlights the complementary use of the titanium-based method and other methods. More results from titanium-catalyzed diastereoselective epoxidation are summarized in Table 25. 

Tetrahedral blue-black compounds [VL4](SCN)3 (L = en or Me4en) were prepared188 from K3[V(NCS)6] and their electronic spectra are comparable to other tetrahedral vanadium(III) complexes with substituted pyridines (see Section 33.4.3.2). 

The chemistry already described is reproduced by numerous ligands that have not specifically been addressed in the previous discussion. The V-salicylidenehydrazides (Scheme 4.18a) and related compounds provide a good example. The structure [76] of a typical complex, represented in Scheme 4.18b, is not very different from that proposed for the solution structures of dipeptide complexes (Scheme 4.17). Interestingly, other similar complexes, based on Schiff base-derived ligands, form dimeric [VO]2 core complexes (Scheme 4.1) via two long ( 2.4 A) VO bonds [2], The cyclic core is not necessary for dimer formation, and a dimer can form via a linear VOV bond [77], These complexes otherwise are not significantly different in their vanadium coordination from that depicted in Scheme 4.18b. 

Studies of the oxidation of organic sulfides with amino acid-derived ligands in acetonitrile revealed very little difference between the mechanism of their oxidation and that of halides, except for one major exception. Despite the fact that acid conditions are still required for the catalytic cycle, hydroxide or an equivalent is not produced in the catalytic cycle, so no proton is consumed [48], As a consequence, there is no requirement for maintenance of acid levels during a catalyzed reaction. Peroxo complexes of vanadium are well known to be potent insulin-mimetic compounds [49,50], Their efficacy arises, at least in part, from an oxidative mechanism that enhances insulin receptor activity, and possibly the activity of other protein tyrosine kinases activity [51]. With peroxovanadates, this is an irreversible function. Apparently, there is no direct effect on the function of the kinase, but rather there is inhibition of protein tyrosine phosphatase activity. The phosphatase regulates kinase activity by dephosphorylating the kinase. Oxidation of an active site thiol in the phosphatase prevents this down-regulation of kinase activity. Presumably, this sulfide oxidation proceeds by the process outlined above. 

In addition to the linear oligomers, cyclic derivatives (V33, V44, V/ ) are also known (see Section 2.2). The latter two are readily formed and are ubiquitous components of aqueous solutions. These compounds are relatively inert to complex-ation reactions that preserve their cyclic structure rather, the equilibria shift towards products of other vanadium stoichiometry. Presumably, one way to generate complexes of these oligomers would be to protonate one or more oxygens so that the reactivity is increased. However, neither protonated V4 nor V5 has been identified in solution, nor has there yet been any indication from studies in alcoholic solution that an alkoxo group can replace an oxo ligand, as might be expected if protonation occurs. 

Carbonyl and other Low Oxidation State Compounds.—Tris-(2,2 -bipyridyl)vana-dium(O) solutions in DMF exhibit three one-electron reduction waves corresponding to VL3 - VL3 (L = 2,2 -bipyridyI) VLJ -> VL " and VLf -VL, and two oxidation waves corresponding to VL3-> VL3 and VLJ ->VL3+ whose half-wave potentials differ by only 0.10 V.342 The difference for the isoelectronic chromium complexes is 0.49 V. An explanation has been offered for the small difference between the vanadium potentials in terms ol the possible diamagnetism of the d4VL3 species arising from a substantial splitting of the l2g orbitals. 

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