Chromium complexes oxides

Entries where the oxidation state of a metal has been specified occur after all the entries for the unspecified oxidation state, and the same or similar entries may occur under both types of heading. Thus cyanide appears under Chromium complexes, Chromium(O) complexes, Chromium(I) complexes, etc. More specific entries, such as Chromium, hexacyano-, may also occur. Similar ligands may also occur in different entries. Thus a carboxylic acid-metal complex may occur under Carboxylic acid complexes, under entries for specific carboxylic acids, and under the specific metal. Coordination complexes may also be listed in the Cumulative Formula Index. 

The fact that pentacarbonyl carbene complexes react with enynes in a chemo-selective and regiospecific way at the alkyne functionality was successfully applied in the total synthesis of vitamins of the Kj and K2 series [58]. Oxidation of the intermediate tricarbonyl(dihydrovitamin K) chromium complexes with silver oxide afforded the desired naphthoquinone-based vitamin K compounds 65. Compared to customary strategies, the benzannulation reaction proved to be superior as it avoids conditions favouring (E)/(Z)-isomerisation within the allylic side chain. The basic representative vitamin K3 (menadione) 66 was synthesised in a straightforward manner from pentacarbonyl carbene complex 1 and propyne (Scheme 38). 

Dipyridiue-chromium(VI) oxide2 was introduced as an oxidant for the conversion of acid-sensitive alcohols to carbonyl compounds by Poos, Arth, Beyler, and Sarett.3 The complex, dispersed in pyridine, smoothly converts secondary alcohols to ketones, but oxidations of primary alcohols to aldehydes are capricious.4 In 1968, Collins, Hess, and Frank found that anhydrous dipyridine-chromium(VI) oxide is moderately soluble in chlorinated hydrocarbons and chose dichloro-methane as the solvent.5 By this modification, primary and secondary alcohols were oxidized to aldehydes and ketones in yields of 87-98%. Subsequently Dauben, Lorber, and Fullerton showed that dichloro-methane solutions of the complex are also useful for accomplishing allylic oxidations.6... 

The chief drawbacks to using the Collins reagent are the nuisance involved in preparing pure dipyridine chromium VI) oxide,6 its hygroscopic nature5 and its propensity to enflame during preparation.2 3 5 The present method avoids these difficulties by simply preparing diehloromethane solutions of the complex directly.7 In... 

Hg " complexes are common, but complexes of Na, Mg", or Al are rare. Chromium complexes are also common, but in such complexes the chromium is in a low or zero oxidation state (which softens it) or attached to other soft ligands. In another application, we may look at this reaction ... 

Complex oxide film is formed in a basic solution, whereas the films described earlier are formed in an acidic solution. Complex oxide conversion coating reactions do not contain either hexavalent or trivalent chromium ions. However, the sealing rinse contains much greater quantities of hexavalent and trivalent chromium ions than do the sealing rinses associated with phosphate conversion coatings and chromate conversion coatings. 

This chromium complex, and the molybdenum and tungsten analogues with two N-oxide ligands, were all explosive [1]. The chromium complex has exploded during desiccation [2],... 

In reactions carried out for 24 h at room temperature, a 95% yield of cyclo-hexanol from cyclohexanone was obtained. Other ketones and aldehydes were also hydrogenated under identical conditions, but with slower rates (38% conversion for hydrogenation of 2-hexanone, 25% conversion of acetophenone, 45% for 3-methyl-2-butanone). Insertion of the C=0 bond of the ketone or aldehyde into the Cr-H bond was proposed as the first step, producing a chromium alk-oxide complex that reacts with acid to generate the alcohol product. The anionic chromium hydride [(COJsCrH]- is regenerated from the formate complex by... 

Another example of an unusual reaction occurring in the gas phase is ammonia in a chromium complex ion being substituted by arenes such as benzene (4). It is important to note the uncommon oxidation state of the chromium. 

An interesting alternative to the use of chromium(VI) oxidants for the conversion of 1 to 2 involves the use of a low-valent iron reagent prepared in situ by the action of hydrogen peroxide on an iron(II) complex of 1 (73). Vinblastine (as the free base) is treated with 2 equiv of perchloric acid in acetonitrile at -20°C. Ferrous perchlorate is then added, followed by the addition of excess 30% hydrogen peroxide. Work-up of the reaction mixture with a saturated solution of ammonium hydroxide gives 2 in yields of 35-50% after chromatography. 

B. General Oxidation Procedure for Alcohols. A sufficient quantity of a 5% solution of dipyridine chromium (VI) oxide (Note 1) in anhydrous dichloromethane (Note 7) is prepared to provide a sixfold molar ratio of complex to alcohol. This excess is usually required for complete oxidation to the aldehyde. The freshly prepared, pure complex dissolves completely in dichloromethane at 25° at 5% concentration to give a deep red solution, but solutions usually contain small amounts of brown, insoluble material when prepared from crude complex (Note 8). The alcohol, either pure or as a solution in anhydrous methylene chloride, is added to the red solution in one portion with stirring at room temperature or lower. The oxidation of unhindered primary (and secondary) alcohols proceeds to completion within 5 minutes to 15 minutes at 25° with deposition of brownish-black, polymeric, reduced chromium-pyridine products (Note 9). When deposition of reduced chromium compounds is complete (monitoring the reaction by gas chromatography or thin-layer chromatography analysis is helpful), the supernatant liquid is decanted from the (usually tarry) precipitate and the precipitate is rinsed thoroughly with dichloromethane (Note 10). 

Uses. In organic oxidations and chlorina-tions as a solvent for chromium oxide in making chromium complexes and dyes... 

A second manufacturing method for acetic acid utilizes butane from the C4 petroleum stream rather than ethylene. It is a very complex oxidation with a variety of products formed, but conditions can be controlled to allow a large percentage of acetic acid to be formed. Cobalt (best), manganese, or chromium acetates are catalysts with temperatures of 50-250 °C and a pressure of 800 psi. 

R. P. Farrell and P. A. Lay, New Insights into the structure and reactions of chromium (V) complexes. Implications for chromium(VI) and chromium(V) oxidations of organic substrates and the mechanism of chromium-induced cancers, Comments Inorg. Chem., 13 (1992) 133-175. 

Chromyl chloride is used in many organic synthetic reactions including oxidation and chlorination. It also is used as a catalyst in olefin polymerization in the preparation of chromium complexes and as a solvent for chromic anhydride. 

Leelasubcharoen S (2001) Pentamethylcyclopentadienyl Chromium Complexes in Ethylene Polymerization and Oxidation Reactions. PhD Thesis, University of Delaware... 

The following procedure can be extended to prepare l-oxacyclopent-2-ylidene chromium complexes substituted in the 3 or 5 position.4 Thus the reaction of the anion of pentacarbonyl(l-methoxypropylidene)chromium(0) with ethylene oxide gives pentacarbonyl [dihydro-3-methyl-2(3//)-furylidene] chromium(O) [pentacarbonyl(3-methyl-l-oxacyclopent-2-ylidene)chromium(P)], and the reaction of the anion of pentacarbonyl(l-methoxyethylidene)chromium(0) with propylene oxide gives pentacarbonyl(dihydro-5-methyl-2(3//)-furanylidene)-chromium(O) [pentacarbonyl(5-methyl-l-oxacyclopent-2-ylidene)chromium(0)]. 

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