Zinc complexes amine oxides

Zeise s salt, 353, 403 Zinc, 925-1022 metallocnzymcs, 1001, 1002 biomimetic modelling, 1021 X-ray crystallography, 1002 zinc-carbonyl mechanism, 1003 zinc-hydroxide mechanism. 1003 Zinc complexes acetate, 969 alcohols, 964 amides, 944 amine oxides, 964 amines, 933 amino acids, 938... 

Because the reactions of related in -cyclohexadienyl complexes are synthetically valuable, the reactions of this ligand have been studied extensively. An outline of how this chemistry can be conducted on the Fe(CO)j fragment is shown in Equation 11.51. A variety of cyclohexadienes are readily available from Birch reduction of substituted aromatics. Coordination and abstraction of a hydride, typically by trityl cation, leads to cationic cyclohexadienyl complexes. These cyclohexadienyl complexes are reactive toward organolithium, -copper, -cadmium, and -zinc reagents, ketone enolates, nitroal-kyl anions, amines, phthalimide, and even nucleophilic aromatic compounds such as indole and trimethoxybenzene. Attack occurs exclusively from the face opposite the metal, and exclusively at a terminal position of the dienyl system. This combination of hydride abstraction and nucleophilic addition has been repeated to generate cyclohexa-diene complexes containing two cis vicinal substituents. The free cyclohexadiene is ttien released from the metal by oxidation with amine oxides. ... 

Activators. Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form mbber soluble complexes. These complexes then react with the sulfur to achieve vulcanization. The most common activators are combinations of zinc oxide and stearic acid. Other metal oxides have been used for specific purposes, ie, lead, cadmium, etc, and other fatty acids used include lauric, oleic, and propionic acids. Soluble zinc salts of fatty acid such as zinc 2-ethyIhexanoate are also used, and these mbber-soluble activators are effective in natural mbber to produce low set, low creep compounds used in load-bearing appHcations. Weak amines and amino alcohols have also been used as activators in combination with the metal oxides. 

Halobutyl Cures. Halogenated butyls cure faster in sulfur-accelerator systems than butyl bromobutyl is generally faster than chlorobutyl. Zinc oxide-based cure systems result in C—C bonds formed by alkylation through dehydrohalogenation of the halobutyl to form a zinc chloride catalyst (94,95). Cure rate is increased by stearic acid, but there is a competitive reaction of substitution at the halogen site. Because of this, stearic acid can reduce the overall state of cure (number of cross-links). Water is a strong retarder because it forms complexes with the reactive intermediates. Amine cure may be represented as follows ... 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3, so-called neutral diazotization) or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. Kozlov and Volodarskii (1969) measured the rates of diazotization of l-amino-2-naphthol-4-sulfonic acid in the presence of one equivalent of 13 different sulfates, chlorides, and nitrates of di- and trivalent metal ions (Cu2+, Sn2+, Zn2+, Mg2+, Fe2 +, Fe3+, Al3+, etc.). The rates are first-order with respect to the added salts. The highest rate is that in the presence of Cu2+. The anions also have a catalytic effect (CuCl2 > Cu(N03)2 > CuS04). The mechanistic basis of this metal ion catalysis is not yet clear. 

Polymeric or monomeric complexes are formed in the reaction between zinc halides and dimethyl(aminomethyl)phosphine oxide dependent on the ratio of reactants. The ligand can bind as bidentate to one metal center or bridge two metal centers through the amine N and phosphine oxide O atoms.851... 

V,/V-bis(2-hydroxy-di-3,5-/-butylphenyl)amine forms complexes of zinc which have ligand-based redox processes with four oxidation levels of the coordinated anion.864 2 1 and 1 1 complexes are formed in the presence of zinc with the 2 1 complex coordinated in an octahedral geometry and the 1 1 complex square planar with a triethylamine ligand completing the coordination sphere. The complexes, at the different redox levels, have been investigated by EPR, spectro-electrochemistry, l I NMR, and magnetochemistry, as appropriate. 

Itoh et al. (151) employed a tetradentate amine and synthesized the complex [Znn(l)(MeCN)]PF6, where 1 represents the monoanion of 2-methylthio-4-ferf-6-[[bis[2-(2-pyridyl)ethyl]amino]methyl]phenol (see Fig. 31 for 1). This complex was chemically [with (NH4)2[Ce(N03)6]) or electrochemically oxidized yielding the (phenoxyl)zinc species Zn1 (1 )(MeCN )]PF6. It displays phenoxyl K-K tran-... 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3) so-called neutral diazotization or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. 

The action of redox metal promoters with MEKP appears to be highly specific. Cobalt salts appear to be a unique component of commercial redox systems, although vanadium appears to provide similar activity with MEKP. Cobalt activity can be supplemented by potassium and zinc naphthenates in systems requiring low cured resin color lithium and lead naphthenates also act in a similar role. Quaternary ammonium salts (14) and tertiary amines accelerate the reaction rate of redox catalyst systems. The tertiary amines form beneficial complexes with the cobalt promoters, facilitating the transition to the lower oxidation state. Copper naphthenate exerts a unique influence over cure rate in redox systems and is used widely to delay cure and reduce exotherm development during the cross-linking reaction. 

Enhancement of fluorescence due to the complexation of metal ions with fluoroionophores has been used as a well-precedented technique to analyze for the presence of metal ions [189-191], A number of studies have reported chelating fluorophores whose emission spectra change upon the addition of metal ions [192-198]. One remarkable result of this emission intensity enhancement is shown in Scheme 23, where the chelation of zinc chloride to 9,10-bis(((2-(dimethylamino)ethyl)methylamino)methyl)anthracene drastically enhances the observed fluorescence by a factor greater than 1000-fold [199], In the absence of Zn2+, the singlet excited state of anthracene moiety is strongly quenched by intramolecular photoinduced electron transfer from the amine to the anthracene moiety. The complex formation of Zn2+ with the amine moiety may result in the largely positive shift of the one-electron oxidation potential. Thus, intramolecular photoinduced electron transfer is strongly suppressed by the complexation of the amine moiety with Zn2+,... 

The electrochemical oxidation of tyramine in NaOH/MeOH media gives films of polytyramine (25). The film, on a platinum electrode, can complex copper(II) ions from aqueous media and cobalt(II), iron(II), manganese(II) and zinc(II) from organic media. X-ray photoelectron spectroscopy established that coordination of the metal ions had occurred. For cobalt, evidence of coordination to both ether and amine functions is obtained, but for the other metal ions evidence of ether coordination is less definitive. 

Treatment of [RuC1(NH3)5]2+ with Ag(02CCF3), followed by zinc amalgam reduction and addition of amine yields [Ru(L)(NH3)5]2+ (L = cyclohexylamine, benzylamine, methylamine).192 Oxidation of these complexes with Br2 produces the corresponding ruthenium(TII) species [Ru(L)(NH3)5]3+.192 Subsequent oxidation of the amine ligand can readily occur to give imine and nitrile products, explaining the relatively few complexes of this type that have been isolated (see Section 45.4.2). 

There are many methods for the desulfurization of nature gas, which can be classified into dry desulfurization, wet desulfurization, and catalytic adsorption. In the dry desulfurization, some solid sorbents, such as iron oxide, zinc oxide, activated carbon (AC), zeolites, and molecular sieves, are used. In wet desulfurization method, liquid-phase chemical/physical solvent absorption systems are usually used for scrubbing H2S amine-based processes are subject to equipment corrosion, foaming, amine-solution degradation, and evaporation, and require extensive wastewater treatment. As a result, this sulfur removal technology is complex and capital intensive,44 although the processes are still employed widely in the industry. The desulfurization of coal gasification gas will be reviewed in detail in Section 5.5. In the catalytic-adsorption method, the sulfur compounds are transformed into H2S by catalytic HDS or into elemental sulfur or SOx by selective catalytic oxidation (SCO), and then, the reformed H2S and SOx are removed by the subsequent adsorption. 

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