Cobalt oxalato

Triphenylsulfonium tetrafluoroborate [(C6Hs)3 S" BF4 ] is used instead of diphenyl iodonium chloride to give phenyl radical as the initiating species. Potassium [tris(oxalato) cobaltate) (III)] with diphenyl iodonium chloride also has been used as the photoinitiator of acryl-... 

Cobalt, tris(oxalato)-racemization solid state, 1, 467 structure, 1, 68... 

Spectra of a variety of chromium compoimds in the +3 valence state are included in Fig. 16. The principal peak is centered at about 22-25 ev. in all cases. The CrjOa spectrum is almost identical to that of Mn02 of Fig. 5. Spectra of the oxalato complex and the ammonia complex are almost identical to spectra of the corresponding cobalt compounds of Figs. 13 and 11. 

The rapid rates of reduction of the oxalato (10) (k = 450 + 1,000 (H+)) and of the pyruvate (2) complexes (2A x 103at 25°C. and (H+) = 0.1) can hardly be understood as caused by chelation. Binoxalate does not chelate unless the proton is lost, and the rate law for the reduction of the complex shows that it brings a proton into the activated complex. Pyruvate almost certainly is not chelated in the product. Both groups are rapidly reduced by Craq.+2 when they are feee from the cobalt center. (The reduction of H2C2O4 by Craq+2 was explored by R. Milburn and the present author (29). The observations on pyruvate were made by R. Butler (2)). The complexes of pyridine-2-carboxylate and pyridine-4-carboxylate are rapidly reduced by Cr+2 at least in the forms which present the nitrogen without associated protons. Radical ion intermediates for these structures are not unreasonable. In fact, a stable free radical derived from AT-ethyl-4-carbethoxypyridinyl has been... 

After the resolution of 1-2-chloro-ammino-diethylenediamino-cobaltie chloride many analogous resolutions of optically active compounds of octahedral symmetry were carried out, and active isomers of substances containing central cobalt, chromium, platinum, rhodium, iron atoms are known. The asymmetry is not confined to ammines alone, but is found in salts of complex type for example, potassium tri-oxalato-chromium, [Cr(Ca04)3]K3, exists in two optically active forms. These forms were separated by Werner2 by means of the base strychnine. More than forty series of compounds possessing octahedral symmetry have been proved to exist in optically active forms, so that the spatial configuration for co-ordination number six is firmly established. 

Tetrammino-salts arc also known in which a divalent acidic radicle takes the place of two monovalent acidic radicles in the diacido-tetram-mino-series, giving rise to efs-compounds such as the earbonato-tetram-mino- and the oxalato-tctrammino-cobaltic salts. 

Oxalato-tetrammino-cobaltic Salts, [Co(NH3)4(C204)]R.—These salts are analogous to the carbonato-salts, and were first described by Jorgensen in 1894. 

Oxalato-tetrammino-cobaltic Chloride, [Co(NH3)4(C204)]C1, is prepared by dissolving chloro-aquo-tetrammino-eobaltic chloride in an aqueous solution of oxalic acid and heating the mixture for some time. The oxalato-compound gradually crystallises from the warm solution, and the crystals are collected and washed on the filter with alcohol until the filtrate is free from chlorine and from oxalic acid. It crystallises in carmine-red six-sided plates if dissolved in concentrated sulphuric acid and concentrated hydrochloric acid is added to the liquid, it is transformed into dichloro-tetrammino-cobaltic chloride. Sodium nitrite and acetic acid convert it into dinitro-tetrammino-cobaltic chloride.1... 

Oxalato -nitro -triammino -cobalt, [Co(NH3)3(C204)(N02)], is prepared from oxalato-aquo-triammino-cobaltic nitrate, [Co(NH3)3 C204.H20]N03, by treating the warm aqueous solution with acetic acid and sodium nitrite. The precipitate formed is filtered, washed, and finally rubbed with dilute sulphuric acid until no more nitrous acid is evolved. It is then collected and washed free from acid with water and alcohol. It crystallises in brick-red shining scales which are almost insoluble in water.3... 

Ammonium Tetranitrito - diammino - cobaltate, [Co(XH3)2 (N02)4]NH4, is prepared from cobaltous chloride by mixing an aqueous solution of the salt with aqueous ammonium-chloride solution, sodium nitrite, and ammonia, and oxidising the mixture by passing air through it for several hours. The solution is allowed to stand in air for some days, when crystals gradually separate. These are collected, washed, and reerystallised from water.3 The substance crystallises in brown rhombic prisms. It is decomposed on treatment with potassium hydroxide with evolution of ammonia, and a cold solution reacts with ammonia in presence of ammonium salts, with formation of flavo-dinitro double salts, of which [Co(NH3)4(N02)2][Co(NH3)2(N02)4] is typical. Oxalic acid transforms it into the oxalato-dinitrito-diammino-salt, [Co(NH3)2(N02)2(C204)]NH4. 

It must be concluded, therefore, that the ligands do not become completely detached from the metal ion in isomerization reactions. Comparable results have been observed in the isomerization95 of potassium diaquodioxalatochromium(III) and the racemization96 of optically active potassium tris(oxalato)chromium(III) when no exchange with free ligand in solution occurs. Thus, although it is not practicable to take advantage of the desirable properties of individual isomers of 2 1 chromium and cobalt complexes of tridentate azo compounds because of the facility with which such compounds isomerize in solution, the technically important unsymmetrical 2 1 complexes are capable of practical application because they show little or no tendency to disproportionate in solution. 

The optical antipodes have been obtained recently by resolution using the (+)D-(ethylenediamine)bis(oxalato)cobalt(III) anion, and have been isolated as the iodide salt.2 The exchange reaction with carbonate and the racemization reaction in aqueous solution have been investigated kinetically.3... 

The catalytic action of CDTA complexes of Fe(III), Ni(II), Cu(II), Cr(in), and Mn(II) on the oxidation of L-ascorbic acid with tris(oxalato)cobaltate has been investigated. The rate is proportional to the concentration of the complex. Fe(III)-CDTA is the best catalyst for the reaction.76... 

Reaction of Cytochrome cimu with Tris(oxalato)cobalt(III) The cytochrome c protein was also used as reductant in a study of the redox reaction with tris (oxalato)cobalt(III).284 Selection of the anionic cobalt(III) species, [Conl(ox)3]3 was prompted, in part, because it was surmised that it would form a sufficiently stable precursor complex with the positively charged cyt c so that the equilibrium constant for precursor complex formation (K) would be of a magnitude that would permit it to be separated in the kinetic analysis of an intermolecular electron transfer process from the actual electron transfer kinetic step (kET).2S5 The reaction scheme for oxidation of cyt c11 may be outlined ... 

Reaction of Cytochrome cIinn with Bis(ferrozine)copper(II) Knowledge of the redox properties of cytochrome c was an encouragement to initiate a kinetics investigation of the reduction of an unusual copper(II) complex species by cyt c11. Ferrozine (5,6-bis(4-sulphonatophenyl)-3-(2-pyridyl)-1,2.4-triazine)286 (see Scheme 7.1), a ligand that had come to prominence as a sensitive spectrophotometric probe for the presence of aqua-Fe(II),19c,287 forms a bis complex with Cu(II) that is square pyramidal, with a water molecule in a fifth axial position, whereas the bis-ferrozine complex of Cu(I) is tetrahedral.286 These geometries are based primarily upon analysis of the UV/visible spectrum. Both complexes are anionic, as for the tris-oxalato complex of cobalt in reaction with cytochrome c (Section 7.3.3.4), the expectation is that the two partners will bind sufficiently strongly in the precursor complex to allow separation of the precursor formation constant from the electron transfer rate constant, from the empirical kinetic data. 

Hexamminecobalt(III) salt cannot be used as a precipitant in the oxalato complex precipitation system because it precipitates as hexamminecobalt(III) oxalate. Besides the hexaureachro-mium(III) salt, hexamminechromium(III), tris(ethylenediamine)cobalt (III) or tris(trimethylenediamine)cobalt(III) salts can be used as precipitants. Hexamminechromium(III) and tris(ethylenediamine) cobalt (III) salts form precipitates with actinide(IV) or (VI) oxalato complex ions, whereas tris(trimethylenediamine)co-balt(III) salt forms precipitates with Th(IV) or U(VI) oxalato complex ions leaving Pu(IV) ion in the supernatant solution.Therefore, this reagent plays the role of both a separating agent and a precipitant and is applicable for the separation of Pu(IV) ion from Th(IV) or U(VI) ion. 

The oxalate system is not useful for the separation of Cm-(III) ion from Am(VI) ion because Am(VI) ion is reduced by oxalate ion and its oxalato complex precipitate like that of U(VI) ion with cobalt(III) complex ion cannot be obtained. 

Because the optically active forms of the (ethylenediamine)bis-(oxalato)cobaltate(III) ion have been, and will continue to be, excellent resolving agents for many cationic cobalt(III) complexes, it is only proper that a detailed resolution procedure be developed to produce both enantiomorphic forms in useful quantities. 

Racemic sodium and calcium (ethylenediamine)bis(oxalato)-cobaltate(III) are prepared by the method given by Dwyer, Reid, and Garvan.1... 

---