Vanadium complexes carboxylates

Another interesting asymmetric epoxidation technique using metal catalysis involves the vanadium complexes of A-hydroxy-[2.2]paracyclophane-4-carboxylic amides (e.g., 19), which serve as catalysts for the epoxidation of allylic alcohols with f-butyl hydroperoxide as... 

Shul pin and coworkers have demonstrated, in several papers, that other peroxo vanadium complexes closely related to 36, containing in the coordination sphere amino acids, nitrogen-containing bases or weak carboxylic acids, are effective oxidants of satnrated and aromatic hydrocarbons. An accnrate account containing this work, together with results related to the use of other transition metals, has appeared and aU the relevant literature can be found there. 

The complexes derived from simple monodentate carboxylates are not stable, and only one mononuclear complex with a sterically hindered carboxylate has been successfully isolated, [VCKCbC Bujs] (13).103 Attempts to prepare carboxylates in organic solvents often led to the formation of oligomeric cluster compounds with a variety of interesting structural types.103 In aqueous solutions, these vanadium complexes appear to contain six-coordinate vanadium.60,104 Even carbonate has been found to form a weak vanadiumtV) complex in solution.105... 

Figure X, 1. Kinetic curves of cyclohexy hydroperoxide (1) formation and its decomposition to yield cyclohexaiiol (2) and cyclohexanone (i) in the oxidation of cyclohexane fO.46 mol dm ) by the reagent O - II1O2 - vanadium complex - pyrazine-2-carboxylic acid in MeCN at 50 (top) and 70 C (bottom).

Picolinic acid also accelerates the H2O2 oxidations but less efficiently than pyrazine-2-carboxylic acid. It has been demonstrated recendy that the vanadium complex with picolinic acid, VO(PA)2 , encapsulated into the NaY zeolite retains solution-like activity in the liquid-phase oxidation of hydrocarbons [16a], It is noteworthy that pyrazine-2-carboxylic acid accelerates the hydrocarbon oxidation catalyzed by CH3Re03 [25 b]. Employing a (+)-camphor derived pyrazine-2-carboxylic acid as a potential co-catalyst in the CHsReOj-catalyzed oxidation of methyl phenyl sulfide with urea-H202 adduct, the corresponding sulfoxide was obtained with an e.e. of 15% [16b]. 

Scheme X.4, The simplified mechanism proposed for the oxidation of alkanes, RH, by the reagent O2 - H2O2 - vanadium complex - pyrazine-2-carboxylic acid .

Nizova, G.V., Shul pin, G.B., Suss-Fink, G., and Stanislas, S. (1998) Carboxylation of methane with CO or CO2 in aqueous-solution catalyzed by vanadium complexes. Chem. Commun., 1885-1886. 

The tert-huty hydroperoxide is then mixed with a catalyst solution to react with propylene. Some TBHP decomposes to TBA during this process step. The catalyst is typically an organometaHic that is soluble in the reaction mixture. The metal can be tungsten, vanadium, or molybdenum. Molybdenum complexes with naphthenates or carboxylates provide the best combination of selectivity and reactivity. Catalyst concentrations of 200—500 ppm in a solution of 55% TBHP and 45% TBA are typically used when water content is less than 0.5 wt %. The homogeneous metal catalyst must be removed from solution for disposal or recycle (137,157). Although heterogeneous catalysts can be employed, elution of some of the metal, particularly molybdenum, from the support surface occurs (158). References 159 and 160 discuss possible mechanisms for the catalytic epoxidation of olefins by hydroperoxides. 

Trinuclear zinc carboxylate structures of the form MZn2(MeCH=CHC02)6(quinoline)2 have been structurally characterized with M = Mn, Co, Ni, Zn, Cd, Mg, Ca, Sr. Structural variation is observed for the group 2 metals. The remaining complexes all show linear trimers with the central metal atom octahedrally coordinated and linked to each zinc by two bidentate and one mono-dentate carboxylate.377 A basic benzoate octanuclear structure with four vanadium(III) and four zinc atoms has been characterized, [VZnO(benzoate)3(TF[F)]4-2TnF.378... 

Ethylene-propylene-diene terpolymers (EPDM), with their inherent complexity in structural parameters, owe their tensile properties to specific structures dictated by polymerization conditions, among which the controlling factor is the catalyst used in preparing the polymers. However, no detailed studies on correlation between tensile properties and EPDM structures have been published (l,2). An unusual vulcanization behavior of EPDMs prepared with vanadium carboxylates (typified by Vr g, carboxylate of mixed acids of Ccj-Cq) has been recently reported Q). This EPDM attains target tensile properties in 18 and 12 minutes at vulcanization temperatures of 150 and l60°C respectively, while for EPDMs prepared with V0Cl -Et3Al2Cl or V(acac) -Et2AlCl, about 50 and 0 minutes are usually required at the respective vulcanization temperatures, all with dieyclopentadiene (DCPD) as the third monomer and with the same vulcanization recipe. This observation prompted us to inquire into the inherent structural factors... 

Unisulf [Unocal sulfur removal] A process for removing sulfur compounds from petroleum fractions, similar to the Stretford process, but including in the catalytic solution vanadium, a thiocyanate, a carboxylate (usually citrate), and an aromatic sulfonate complexing agent. Developed by the Union Oil Company of California in 1979, commercialized in 1985, and operated in three commercial plants in 1989. 

The reduction of carboxylatopentamminecobalt(III) complexes by vanadium(II) is predominantly inner-sphere.163 From [Co(en)(C204)2]- and [CofQO ]3-, (0204) and V3+ ions are primary products.164 tor N-bonded glycinato- and /3-alaninato-penta-amminecobalt(III), there is an intermediate with V11 attached to the unprotonated carboxylate group.165... 

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