Cobalt iodide complex

Decomposition of most cobalt(III) complexes by boiling with alkali gives a brown precipitate of the hydrated oxide C02O3. aq (p.402). This will quantitatively oxidise iodide to iodine. 

Palladium complexes also catalyze the carbonylation of halides. Aryl (see 13-13), vinylic, benzylic, and allylic halides (especially iodides) can be converted to carboxylic esters with CO, an alcohol or alkoxide, and a palladium complex. Similar reactivity was reported with vinyl triflates. Use of an amine instead of the alcohol or alkoxide leads to an amide. Reaction with an amine, AJBN, CO, and a tetraalkyltin catalyst also leads to an amide. Similar reaction with an alcohol, under Xe irradiation, leads to the ester. Benzylic and allylic halides were converted to carboxylic acids electrocatalytically, with CO and a cobalt imine complex. Vinylic halides were similarly converted with CO and nickel cyanide, under phase-transfer conditions. ... 

The relatively minor alteration in reaction conditions can be seen to drastically alter the nature of the product (468). In addition many sulfoxide complexes are thermally degraded, and in consequence the extent of drying can alter the nature of the product. Thus, the complex [Co(0-Me2SO)8][I]2 is isolated from a cobaltous iodide-dimethyl sulfoxide system, but extensive drying in vacuo causes degradation to yield [Co(0-Me2SO)6][CoI4] (128). 

It has been reported ( ) that homogeneous ruthenium- or cobalt-iodide-based complexes catalyze the homologation of esters of carboxylic acid to their next higher homologues, for instance ... 

Photoreduction of cobalt(III) complexes can occur under a variety of conditions. Irradition of the charge transfer bands of these systems results only in decomposition with production of cobaltous ion and oxidation of one of the ligands. In some instances photoreduction can be initiated by irradiation of the ligand field transitions. Irradiation of ion pairs formed by these complexes with iodide ion with ultraviolet light also leads to reduction of the complexes. Finally, irradiation of iodide ion in the presence of the complexes leads to reduction. 

Photolysis of ion pairs of cobalt(III) complexes with iodide ions leads to oxidation of iodide and reduction of the complex.55,63-86 Under the normal experimental conditions, however, most of the light is absorbed by free iodide and the reduction of the complex is effected by hydrated electrons produced as in reaction (36).86... 

I wish to point out that these reactions were studied in either neutral or acidic solutions where the cyanide cobalt system is really unstable thermodynamically. I raise the question about oxidation-reduction in the iodo complex. This wasn t mentioned in the paper. It seems to me it would provide an alternate path which might increase the reaction rates in the case of the iodide complex. 

Other cobalt(III) complexes showing soft behaviour with preference for cyanide, iodide and alkyl ligands are the cobalamine group of vitamin B 1260 and the bis (di-methylglyoximates) involving four nitrogen atoms bound in the equatorial plane in both cases, as is true for porphyrin and chlorophyll complexes. 

Rusling et al. performed electrochemically and light mediated radical additions of alkyl iodides to cyclohexenone in conductive microemulsions catalyzed by 20 mol% of 247 in 14—81% yield [303]. Radical allylations of alkyl bromides 249 with allyl sulfides, sulfones, or phosphates catalyzed by 5 mol% of cobalt (iminate) complex 250 in the presence of zinc as reducing agent proceeded in 52-85% yield [304],... 

In 1968 Monsanto reported a chemically related process based on rhodium iodide complexes. Due to its high reaction rates, high selectivity and different kinetics, the process differs substantially from the cobalt process. Commercialization was achieved in 1970. Operating conditions are remarkably mild 30 bar, 180°C. 

The high selectivity of the reaction of cobalt-carbene complexes with alkynes for furan products was taken advantage of in the synthesis of bovolide, a natural flavor constituent of butter. The carbene complex (230) was prepared in two steps from n-pentanal and was treated with 3 equiv. of 2-butyne. The crude reaction mixture, which presumably contained the furan (231), was treated directly with 3 equiv. of trimethylsilyl iodide to give bovolide in - 50% yield from carbene complex (230). 

The ruthenium-cobalt bimetallic complex system catalyzes the homologation of methanol with carbon dioxide and hydrogen in the presence of iodide salts. A synergistic effect is found between these two metals. The yield of ethanol is also affected by the Lewis acidity of the iodide salt, lithium iodide being most effective. The reaction profile shows that methanol is homologated with CO formed by the hydrogenation of CO2. 

Albeit with less overall success, trifluoromethyl iodide has also been employed to effect oxidative trifluoromethylations of elemental copper and a few chromium and cobalt coordination complexes and to oxidatively cleave metal—metal bonds in complexes like Ni2(CO)2(Cp)2, Co2(CO)g, and GeMe3Fe(CO)2Cp. One of the first examples of this type of reaction is (22)... 

Pyrazolin-5-ones react with salts of various metals to form compounds in which the pyrazolinone has reacted in its enolic form with replacement of the enolic hydrogen to give a salt and having semipolar bonds formed by donation of electrons to the metal by the nitrogen atoms393 394 Usually these compounds contain the number of pyrazolinone residues corresponding to the valence of the metal atom. Such salts as cuprous iodide, ferric iodide, cobaltous iodide, silver iodide and silver diiodide participate in such reactions.393,394 In addition, complexes may be formed in which there has been no elimination of a small molecule between the reactants and no formation of ionic bonds.432... 

The reactivity of the catalyst is enhanced by azeotropic drying of the cobalt complex before use, thus allowing the reaction of sterically hindered and silyl-substituted alkynes. Good reactivity between norbornadiene and disubstituted alkynes (yields in homo-Diels-Alder adducts ca. 85%) is also achieved by adding zinc powder to cobalt iodide/triphenylphosphane catalysts. " ... 

Among the latest developments arc the carbonylation of methyl acetate to acetic anhydride in the presence of cobalt iodide or bromide (BASF) or of rhodium and methyl iodide base complexes (Eastman Kodak/Halcon, Showa Denko, etc.). 

The TTX complexes, tmro-[CoCl2(TTX)] (CIO4) and traw-[CoBr2(TTX)] CIO4, are prepared by allowing [Co(TTX)] ( 104)2 to react with an appropriate lithium halide in nitromethane. Reaction of [Co(TTX)] ( 104)2 with lithium iodide produces the cobalt(II) complex, [ ol2(TTX)]. 

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