VO acac

1 VO(acac)2. - An ab initio calculation was completed to determine the equilibrium geometry of this metal complex. For this calculation and our subsequent calculations, the acetylacetonate ligand was approximated by the (acac ) ligand which shows the methyl groups replaced by hydrogens so as to decrease the time required to complete the calculations. This simplification has been found satisfactory in previous studies The predicted equilibrium structure shows the (acac ) ligands were bent away from a plane that is perpendicular to the V = Obond (Fig. 2). 

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Catalysts VO(acac)2 Mo(CO)e Ti(OiPr)4 Oxidant tBuOOH PhC(CH3)200H... 

Donor strengths, taken from ref. 207b, based upon the solvent effect on the symmetric stretching frequency of the soft Lewis acid HgBr2. Gutmann s donor number taken from ref 207b, based upon AHr for the process of coordination of an isolated solvent molecule to the moderately hard SbCL molecule in dichioroethane. ° Bulk donor number calculated as described in ref 209 from the solvent effect on the adsorption spectrum of VO(acac)2. Taken from ref 58, based on the NMR chemical shift of triethylphosphine oxide in the respective pure solvent. Taken from ref 61, based on the solvatochromic shift of a pyridinium-A-phenoxide betaine dye. 

Five-coordinate complexes are far more common than was once supposed and are now known for all configurations from d to d. Two limiting stereochemistries may be distinguished (Fig. 19.4). One of the first authenticated examples of 5-coordination was [VO(acac)2] which has the square-pyramidal 4 structure with the =0 occupying the unique apical site. However, many of the complexes with this coordination number have structures intermediate between the... 

The parent indolo[2,3-fl]carbazole (1) has also been the subject of a study probing its reactivity toward oxidizing agents. One of the substrates involved, namely 85 (prepared from 1 and 2,5-dimethoxytetrahydrofuran in the presence of acid), was subjected to treatment with m-chloroperbenzoic acid, to give the dione 86 as the major product and a sensitive compound assigned the hydroxy structure 87. A cleaner reaction took place when 85 underwent oxidation with tert-butyl hydroperoxide assisted by VO(acac)2, to produce 86 exclusively in 86% yield. Likewise, A,N -dimethylindolo[2,3-fl]carbazole furnished the dione 88 on treatment with this combination of reagents (96J(X 413). 

Tetrahydropyran- and tetrahydrofuran-substituted rings are common in many complex natural products, such as polyether antibiotics, displaying a wide range of biological properties [4]. An appropriate combination of OH-directed diastereose-lective epoxidation of y- and 8-alkenols [VO(acac)2/TBHP or MCPBA] [5] or ster-... 

For the formation of substituted THF rings (Route a, Scheme 8.1), Kishi developed a procedure based on the hydroxy-directed epoxidation of a y-alkenol [10]. Epoxidation of bishomoallylic alcohol 3 by TBHP/VO(acac)2 by this approach, followed by treatment of the intermediate epoxide 4 with acetic acid, gave the TH F derivative 5 of isolasalocid A (a 5-exo cydization Scheme 8.2) [11]. Further epoxidation of 5 (a y-alkenol) under the same conditions, followed by acetylation, afforded epoxide 6. For the synthesis of the natural product, the configuration of epoxide 6 had to be inverted before the second cydization reaction. Epoxide 6 was consequently hydrolyzed under acid conditions to the corresponding diol and was then selectively... 

The structure of glabrescol was subsequently revised, and the new structure was synthesized enantioselectively through sequential hydroxy-directed anti-oxidative cyclization of acyclic y-alkenols with VO(acac)2/TBHP to construct the adjacent THF rings via epoxides under acid conditions [35b],... 

Vinylepoxides can be obtained by various strategies, all with their inherent limitations. Racemic epoxidation of olefins is a straightforward route to epoxides, as pure trans- or cis-epoxides can be obtained from ( )- or (Z)-alkenes, respectively. Various oxidants - such as mCPBA and other peracids, H2O2, or VO(acac)2/TBHP - can all be employed in this transformation [1],... 

In a.p. ZV(a) and ZV(i) samples, broad bands arising from hydrated vanadates were detected in the 800-1100 cm-i region. Metavanadate-like species (band at 920 cm i) prevailed on ZV samples with V-content < 1.5 atoms nm 2 and decavanadates (bands at 850-880 cm i and 960-990 cm- ) in the range 1.5-3 atoms nm 2. A.p. ZV(acac) samples showed bands from CH3 and C=0, suggesting the adsorption of VO(acac)2 as such (spectra not reported). 

Sn/V/Nb/Sb/0 catalysts were prepared with the co-precipitahon technique, developed for the synthesis of ratile Sn02-based systems claimed by Rhodia (8). The preparation involved the dissoluhon of SnCl45H20, VO(acac)2, SbCh and NbCls in absolute ethanol, and by dropping the soluhon into a buffered aqueous soluhon maintained at pH 7. The precipitate obtained was separated from the liquid by filtrahon. The solid was then dried at 120°C and calcined in air at 700°C for 3 hours. The V/Sb/0 catalyst was prepared by means of the slurry method that consists in a redox reachon between Sb203 and NH4VO3 in water medium, for 18h at 95°C. The... 

Table 5.2 Equilibrium and rate constants for VO(acac)2-Base exchange.

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