Ethylenediamine chromium complexes

Balthis and Bailar6 obtained tris (ethylenediamine) chromium-(III) complexes by the oxidation of chromium(II) solutions, using a procedure somewhat similar to that used for the synthesis of cobalt (III) com plexes. Mori7 described the preparation of hexaamminechromium(III) salts from the oxidation of chromium (II) salts in the presence of ammonia. The results obtained in both syntheses have been erratic.8,9 Berman noted that the foregoing syntheses are rendered dependable by the use of a catalyst of activated platinum on asbestos. Schaeffer,100 in a subsequent study, independently used colloidal platinum as a catalyst but reported some difficulty in separating it from the product.106 The procedures recommended and described here are based on the use of platinized asbestos as the catalyst. 

The adsorption of transition metal complexes by minerals is often followed by reactions which change the coordination environment around the metal ion. Thus in the adsorption of hexaamminechromium(III) and tris(ethylenediamine) chromium(III) by chlorite, illite and kaolinite, XPS showed that hydrolysis reactions occurred, leading to the formation of aqua complexes (67). In a similar manner, dehydration of hexaaraminecobalt(III) and chloropentaamminecobalt(III) adsorbed on montmorillonite led to the formation of cobalt(II) hydroxide and ammonium ions (68), the reaction being conveniently followed by the IR absorbance of the ammonium ions. Demetallation of complexes can also occur, as in the case of dehydration of tin tetra(4-pyridyl) porphyrin adsorbed on Na hectorite (69). The reaction, which was observed using UV-visible and luminescence spectroscopy, was reversible indicating that the Sn(IV) cation and porphyrin anion remained close to one another after destruction of the complex. 

Thermal deamination of tris(ethylenediamine)chromium(III) complexes is a standard preparative method for cis- and trans-diacidobis(ethylenediamine) complexes421,422 and the thermal behaviour of the starting materials has been related to their crystal structures.423 The cyano complex cis-[Cr(CN)2(en)2]C104 in DMSO undergoes stepwise reduction III— 11 — I at the DME. The standard redox potential for the Cr /Cr11 couple is -1.586 V (versus SCE). 

The three different tetranuclear structures which have been observed in the crystalline state are the two compact structures 6 and 8 and the chain structure 7a. Structure 6 is found in [Co4(NH3),2(OH)6]C16-8H20 and its amine analogs (52 59). The analogous ammonia and ethylenediamine chromium(III) complexes Cr4(NH3)12(OH)66+ and Cr4(en)6(0H)66+ have been characterized quite recently (40, 41, 42, 60). Structure 7a has so far been observed (42) only in a chromium(III) amine complex, Cr4(en)6(OH)66+, but, as discussed in Section IV, both structures 7b and 7c are possible structures for the tetranuclear aqua chromium(III) species. Structure 8 is known from the so-called rhodoso complex, Cr4N12(OH)66+ [N12 = (NH3)12 or (en6] (61, 62). 

The tris(ethylenediamine) chromium (III) ion was first resolved by Werner6 by means of sodium 3-nitro-(+)-camphor. What has been said concerning the resolution of the corresponding rhodium compound holds true of the chromium compound, except that for the chromium compound the solubility difference of the diastereoisomeric chloride (+)-tartrates is so small that a resolution via these diastereoisomers has not been achieved.5,6 The method reported here is essentially the same as the one described for the rhodium complex but with minor alterations... 

It has been found4 that a good yield may be obtained rapidly by allowing the commercially available green chromic chloride, CrCl8-6H20, in methanol to boil under reflux with ethylenedi-amine in the presence of metallic zinc. The product, hydrated tris(ethylenediamine)chromium(III) chloride, is obtained as a solid and is readily purified. An exactly similar procedure may be used for the complex of 1,2-propanediamine. 

Solutions of chromium bis(ethylenediamine)diacetate complex in methanol are capable of reducing simple a,p-unsaturated ketones to the corresponding saturated ketones. Useful yields are obtained provided a proton donor (AcOH) and a good hydrogen donor (BuSH) are present in the reaction mixture (Scheme 16). ... 

Methods for the preparation and purification of salts of the dimeric complex ions di-/i-hydroxo-bis[tetraamminechromium(III)] and di-p-hydroxo-bis [bis-(ethylenediamine)chromium(III)] and of the two corresponding cobalt(III) species are presented. The two ammine complex dimers are isolated as bromide and perchlorate salts. The two ethylenediamine complexes are isolated as dithionate, bromide, chloride, and perchlorate salts. All four dimers have been obtained by heating the corresponding cis-aquahydroxo complexes as the dithionate salts. 

Other amphiphilic cobalt(III) complexes were reported by Yashiro et al. [192] (Figure 106A) who measured the cmc to be at very low concentrations (3.3 X 10 moldm ) in water but did not report any mesophase formation, and by ourselves demonstrating lyotropic mesophases in surfactant ethylenediamine-based complexes including those of chromium (Figure 106B) [193]. 

The chromium (III) ammines closely resemble the corresponding cobalt(III) complexes in many respects. For example, analogous compounds in the two series are usually isomorphous and of similar color. While the preparative methods used for cobalt (III) ammines can sometimes be employed for the preparation of the corresponding chromium (III) ammines, other methods are usually preferred. Thus a mixture of a chromium (II) salt and ethylenedia-mine absorbs atmospheric oxygen even more readily than does a mixture of a cobalt (II) salt and the base. The procedure for preparing tris(ethylenediamine)chromium(III)... 

A considerable amount of kinetic and mechanistic data has been reported for the base hydrolysis of cis- and trans-dihalobis(ethylenediamine)-cobalt(III) cations/ On the other hand, the only chromium(III) analogs which have been studied are cis- and trans-dichlorobis(ethylenediamine)-chromium(III) cations/ The present study was undertaken to gain additional base hydrolysis data for dihalobis(ethylenediamine)chromium(III) complexes, which will permit a more meaningful comparison with their cobalt(III) analogs. 

Ethylene, with p-methoxyphenyl-acetyl chloride and aluminum chloride to give 6-me thoxy-g-tetralone, 51, 109 Ethylenediamine, complexes with chromium(II) salts,... 

Chromiain(ii) Complexes.—The oxidation of chromium(ii) in alkaline solution has been studied polarographically and the reaction shown to be irreversible with = — 1.65 V vs. S.C.E. In the presence of nitrilotriacetic acid, salicylate, ethylenediamine, and edta the values were determined as —1.075, —1.33, — 1.38, and —1.48 V, respectively. The production of [Cr(edta)NO] from [Cr (edta)H20] and NO, NOJ, or NO2 suggests that this complex is able to react via an inner-sphere mechanism in its redox reactions. ... 

Equilibrium studies have shown that the first formation constant of the chromium(iii)-ethylenediamine system is < 10, over 10 -fold smaller than the value (10 ) previously reported. [Cr(en)3 (tn) ] (x = 0—3 and tn = tri-methylenediamine) complexes have been prepared and resolved using nitro-(-f )D-camphor. These mixed complexes have the same absolute configuration, A, as the pure [Cr(en)3] and [Cr(tn)3] species. Selective intervention of an optically active counterion in the relaxation processes of excited enantiomeric complexes can lead to partial resolution. This has been achieved for [Cr(phen)3] using D-tartrate. ... 

Chromium has a maximum co-ordination number of six the chromium atom, therefore, may combine with, at most, six monovalent atoms or groups, over and above its ordinary valency value, with formation of a complex radicle. Hence chromic chloride is capable of associating with, or adding on, six molecules of ammonia with formation of the derivative, [Cr(NH3)8]Cl3. Ammonia may be replaced by a substituted ammonia group or some other basic group, such as alkyl amine, pyridine, or ethylenediamine. 

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