Chromium complexes, metalation

MORDANT. A substance capable uf binding a dye to a textile liber. The mordant forms an insoluble lake in the liber, the color depending on the metal of the mordant. The most itnponanL mordants are trivaleni chromium complexes, metallic hydroxides, tannic acid. etc. Mordants are used with acid dyes, basic dyes, direct dyes, and sulfur dyes. Prcmetallized dyes contain chromium in the dye molecule. A mordant dye is a dye requiring use of a mordant 10 be effective. See also Dyes. 

Chromium complexes of long-chain fatty acids are exceUent water repeUents which are also used for their food-release properties in certain packaging appHcations. The presence of chromium has raised environmental concerns, despite the fact that the metal is in the trivalent rather than in the highly toxic hexavalent state. This material is available as Qudon (DuPont). 

These siUca-supported catalysts demonstrate the close connections between catalysis in solutions and catalysis on surfaces, but they are not industrial catalysts. However, siUca is used as a support for chromium complexes, formed either from chromocene or chromium salts, that are industrial catalysts for polymerization of a-olefins (64,65). Supported chromium complex catalysts are used on an enormous scale in the manufacture of linear polyethylene in the Unipol and Phillips processes (see Olefin polymers). The exact stmctures of the surface species are still not known, but it is evident that there is a close analogy linking soluble and supported metal complex catalysts for olefin polymerization. 

Methylthiophene is metallated in the 5-position whereas 3-methoxy-, 3-methylthio-, 3-carboxy- and 3-bromo-thiophenes are metallated in the 2-position (80TL5051). Lithiation of tricarbonyl(i7 -N-protected indole)chromium complexes occurs initially at C-2. If this position is trimethylsilylated, subsequent lithiation is at C-7 with minor amounts at C-4 (81CC1260). Tricarbonyl(Tj -l-triisopropylsilylindole)chromium(0) is selectively lithiated at C-4 by n-butyllithium-TMEDA. This offers an attractive intermediate for the preparation of 4-substituted indoles by reaction with electrophiles and deprotection by irradiation (82CC467). 

C02 Chemical Precipitation - Sulfide C09 Chemical Precipitation - Other Cl 1 Neutralization C21 Chromium Reduction C31 Complexed Metals Treatment (other than pH Adjustment)... 

Chromium lignosulfonates are the biggest contributions to heavy metals in drilling fluids. Although studies have shown minimal environmental impact, substitutes exist that can result in lower chromium levels in muds. The less used chromium lignites (trivalent chromium complexes) are similar in character and performance with less chromium. Nonchromium substitutes are effective in many situations. Typical total chromium levels in muds are 100-1000 mg/1. 

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. 

Pyrazolone, l(4-bromophenyl)-3-methyl-4-(2-methyl-6-carboxyphenylazo)-chromium complex geometrical isomerism, 6, 69 5-Pyrazolone, o-carboxyarylazo-metal complexes geometrical isomerism, 6,68... 

A transmetalation of the styrylcarbene chromium complex 62 in the presence of stoichiometric amounts of [Ni(cod)2] to give the nickel carbene intermediate 63 was applied to the synthesis of Cr(CO)3-coordinated cycloheptatriene 64 upon reaction with terminal alkynes [57] (Scheme 37). The formation of pen-tacarbonyl(acetonitrile)chromium is expected to facilitate the metal exchange. 

After these subcategorization bases were evaluated, raw waste characterization was selected as the basis for subcategorization. The raw waste characterization is divided into two components, inorganic and organic wastes. These components are further subdivided into the specific types of wastes that occur within the components. Inorganics include common metals, precious metals, complexed metals, hexavalent chromium, and cyanide. Organics include oils and solvents. 

Table 9.2 lists the unit operations associated with each of the seven industry subcategories (raw waste characteristics). Common metals are found in the raw waste of all 44 unit operations. Precious metals are found in only seven unit operations complexed metals are found in three unit operations hexavalent chromium is found in seven unit operations and cyanide is found in eight unit operations. Within the organics, oils are found in 22 unit operations and solvents are found in nine unit operations. A unit operation will often be found in more than one subcategory. 

Good non-colored negative charging CCAs have been obtained by making non-colored analogues of the 2 1 chromium complex azo dyes. This is achieved by making the metal complex of an aromatic ortho-hydroxy carboxylic acid. Typical examples are the chromium, aluminum, and zinc complexes of di-tert-butyl salicylic acid, e.g., BONTRON E-8136 41 (53) and BON-acid36,41,42 e.g., BONTRON E-82 (54). 

Cycloaddition of the carbene chromium complexes 97 with CO incorporation provides a versatile method for naphthol synthesis, in which the metallacy-clic intermediates 99 are involved [47]. An alternative entry to 101 is achieved by metal carbonyl-catalyzed rearrangement of the cyclopropenes 98 via the same metalla-cyclobutenes 99 and vinylketene complexes 100 [52], Mo(CO)6 shows a higher activity than Cr(CO)6 and W(CO)6. The vinylketene complex 103 is formed by the regioselective ring cleavage of 1,3,3-trimethylcyelopropene 102 with an excess of Fe2(CO)9 [53]. (Scheme 35 and 36)... 

Whether [6]radialenes have a potential as novel ligands for metal complexes remains to be seen. A first example of a successful complexation is provided by 150, which reacts with tris(acetonitrile)tricarbonylchromium in dioxane at room temperature to give the ortho-xylylene chromium complex 175 in excellent yield (83%) (equation 23)105. 

Merlic demonstrated the direct, non-photochemical insertion of carbon monoxide from acylamino chromium carbene complexes 14 to afford a presumed chromium-complexed ketene 15 <00JA7398>. This presumed metal-complexed ketene leads to a munchnone 16 or munchnone complex which undergo dipolar cycloaddition with alkynes to yield the pyrroles 17 upon loss of carbon dioxide. 

Mordant dyes are notoriously troublesome from the viewpoint of colour matching because the hue of the chromium complex usually differs greatly from that of the unmetallised parent dye (section 5.4.1). If other metal ions are present in the treatment bath or on the fibre during chroming, the colour obtained is likely to differ from that of the pure chromium complex. Certain important chrome dyes, including Cl Mordant Black 11 (3.29) and Black 17 (3.30), are particularly sensitive to traces of iron or copper. The hue of the black dyeings obtained is redder in the presence of copper and browner with iron contamination. The fastness to light and wet treatments may also prove inferior under these conditions. Even certain 1 2 metal-complex acid dyes show similar effects in the presence of these impurities,... 

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