Manganese with amines

Mn2(H2P202)2) is the stable product in the potentiometric deterrnination of manganese. Manganese(III) does not coordinate with amines or nitro complexes, but it does make manganicyanides of the types M2(Mn(CN)g) and M2(Mn(CN) (OH)), which are similar to the ferricyanides. The K", Na", LC and manganicyanides have been prepared and slowly hydroly2e in water to MnO(OH). 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

A study of the role of base and ligand in the isomerization of manganese-coordinated conjugated alkynyl carbonyls to the corresponding allenyl carbonyls shows that manganese requires a ligand prior to isomerization with amine bases and the efficacy of these bases correlates with p Ka (Scheme 97). Potassium /-buloxide led to rapid isomerization in the absence of added ligand.140... 

Metal-ion catalysis has been extensively reviewed (Martell, 1968 Bender, 1971). It appears that metal ions will not affect ester hydrolysis reactions unless there is a second co-ordination site in the molecule in addition to the carbonyl group. Hence, hydrolysis of the usual types of esters is not catalysed by metal ions, but hydrolysis of amino-acid esters is subject to catalysis, presumably by polarization of the carbonyl group (Kroll, 1952). Cobalt (II), copper (II), and manganese (II) ions promote hydrolysis of glycine ethyl ester at pH 7-3-7-9 and 25°, conditions under which it is otherwise quite stable (Kroll, 1952). The rate constants have maximum values when the ratio of metal ion to ester concentration is unity. Consequently, the most active species is a 1 1 complex. The rate constant increases with the ability of the metal ion to complex with amines. The scheme of equation (30) was postulated. The rate of hydrolysis of glycine ethyl... 

The arene manganese tricarbonyl cations undergo a reversible reaction with amines giving neutral carboxamido derivatives 14) ... 

The same reactions carried out with the manganese(III) porphyrins 2 and 4 with amines 6, 8 and 12 gave good yields of the nitroderivatives 6a and 8a, but longer reaction times were requested (2 and 5 h, respectively). Comparison with the ferric system yields shows that both manganese(III) complexes 2 and 4 are less efficient in the oxidation of the aromatic amines to the corresponding nitroderivatives. 

Carter CJ, Miller WJ, Neathery MW, Gentry RP, Stake PE, Blackman DM (1974) Manganese metabolism with oral and intravenous Mn in young calves as influenced by supplemental manganese. J. Amin. Sci 38 1284-1290 Duncan JR, Hurley LS (1978) Intestinal absorption of zinc a role for a zinc-binding ligand in milk. Am. J. Physiol 235 556-559... 

Divalent copper, cobalt, nickel, and vanadyl ions promote chemiluminescence from the luminol—hydrogen peroxide reaction, which can be used to determine these metals to concentrations of 1—10 ppb (272,273). The light intensity is generally linear with metal concentration of 10 to 10 M range (272). Manganese(II) can also be determined when an amine is added to increase its reduction potential by stabili2ing Mn (ITT) (272). Since all of these ions are active, ion exchange must be used for deterrnination of a particular metal in mixtures (274). 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

At the end of the reaction time there was no unreacted amine as shown by the following test A 10-ml. aliquot was filtered through Supercel to remove the manganese dioxide, and the filtrate was added to a mixture of 25 ml. of benzene and 25 ml. of water. Extraction of the benzene layer with 10% hydrochloric acid, followed by the addition of sodium hydroxide, gave no oil layer or characteristic odor of the free amine. 

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