Cobalt couple

With the addition of a small concentration of iodide to the noniodine couple. With the addition of a small concentration of DMPPD to the cobalt couple,... 

The difference in the self-exchange rates of the two cobalt couples favors the oxidative pathway by a factor of 300. (For a further discussion of the above and other self-exchange rates, see B. S. Brunschwig, C. Creutz, D. H. Macartney, T.-K. Sham, and N. Sutin, Faraday Discuss. Chem. Soc., No 74, in press). Evidently the difference in the intrinsic barriers is large enough to compensate for the less favorable driving force for the oxidative pathway. As a result the latter pathway can compete favorably with the reductive pathway. 

However, Samsel and Kochi concluded from a detailed mechanistic study that a chain mechanism analogous to group transfer (rather than radical-cobalt coupling) was operative in the cyclization of hexenylcobalt compounds to cyclopentylmethyl isomers. E. G. Samsel and J. K. Kochi, J. Am. Chem. Soc., 1986,108, 4790. 

Dimethyl maleate undergoes a stereospecific cyclopropanation in the presence of a zinc-cobalt couple, but a ciS trans mixture is obtained with zinc-nickel.238 Cyclopropanation of a phosphorus-phosphorus double bond was reported from diiodomethane and zinc to give a diphosphirane (Eq. 53) 239... 

The 3.8-nonadienoate 91, obtained by dimerization-carbonylation, has been converted into several natural products. The synthesis of brevicomin is described in Chapter 3, Section 2.3. Another royal jelly acid [2-decenedioic acid (149)] was prepared by cobalt carbonyl-catalyzed carbonylation of the terminal double bond, followed by isomerization of the double bond to the conjugated position to afford 149[122], Hexadecane-2,15-dione (150) can be prepared by Pd-catalyzed oxidation of the terminal double bond, hydrogenation of the internal double bond, and coupling by Kolbe electrolysis. Aldol condensation mediated by an organoaluminum reagent gave the unsaturated cyclic ketone 151 in 65% yield. Finally, the reduction of 151 afforded muscone (152)[123]. n-Octanol is produced commercially as described beforc[32]. 

Copper sulfate, in small amounts, activates the zinc dust by forming zinc—copper couples. Arsenic(III) and antimony(TTT) oxides are used to remove cobalt and nickel they activate the zinc and form intermetaUic compounds such as CoAs (49). Antimony is less toxic than arsenic and its hydride, stibine, is less stable than arsine and does not form as readily. Hydrogen, formed in the purification tanks, may give these hydrides and venting and surveillance is mandatory. The reverse antimony procedure gives a good separation of cadmium and cobalt. 

Of these dyes, Acid Yellow 151 (37) still has the greatest market among the yellows. As reported by USITC, production had increased to 1989 tons in 1985 from 706 tons in 1975. It is produced by coupling diazotized 2-amino-l-phenol-4-sulfonamide to acetoacetanilide followed by metallizing with cobalt to obtain a 1 2 cobalt complex. Acid Orange 24 (38), which is sulfanilic acid coupled to resorcinol to which diazotized mixed xyUdines have been coupled, is an unsymmetrical primary diasazo dye with a bihinctional coupling component. 

Prepa.ra.tlon, There are several methods described in the Hterature using various cobalt catalysts to prepare syndiotactic polybutadiene (29—41). Many of these methods have been experimentally verified others, for example, soluble organoaluminum compounds with cobalt compounds, are difficult to reproduce (30). A cobalt compound coupled with triphenylphosphine aluminum alkyls water complex was reported byJapan Synthetic Rubber Co., Ltd. (fSR) to give a low melting point (T = 75-90° C), low crystallinity (20—30%) syndiotactic polybutadiene (32). This polymer is commercially available. 

In this work ion-exchange and gel-permeation chromatography coupled with membrane filtration, photochemical oxidation of organic metal complexes and CL detection were applied to the study of the speciation of cobalt, copper, iron and vanadium in water from the Dnieper reservoirs and some rivers of Ukraine. The role of various groups of organic matters in the complexation of metals is established. 

Samples Analyzed by Inductively Coupled Plasma (ICP) Metals — Where two or more of the following analytes are requested on the same filter, an ICP analysis may be conducted. However, the Industrial Hygienist should specify the metals of interest in the event samples cannot be analyzed by the ICP method. A computer print-out of the following 13 analytes may be typically reported Antimony, Beryllium, Cadmium, Chromium, Cobalt, Copper, Iron, Lead, Manganese, Molybdenum, Nickel, Vanadium, Zinc. Arsenic — Lead, cadmium, copper, and iron can be analyzed on the same filter with arsenic. 

Anilines have been reduced successfully over a variety of supported and unsupported metals, including palladium, platinum, rhodium, ruthenium, iridium, (54), cobalt, and nickel. Base metals require high temperatures and pressures (7d), whereas noble metals can be used under much milder conditions. Currently, preferred catalysts in both laboratory or industrial practice are rhodium at lower pressures and ruthenium at higher pressures, for both display high activity and relatively little tendency toward either coupling or hydrogenolysis,... 

The successful clinical use of titanium and cobalt-chromium alloy combinations has been reported Lucas etal. also investigated this combination using electrochemical studies based on mixed potential and protection potential theories. Verification of these studies was made by direct coupling experiments. The electrochemical studies predicted coupled corrosion potentials of -0.22 V and low coupled corrosion rates of 0.02 ft A/cm. Direct coupling experiments verified these results. The cobalt-titanium interfaces on the implants were macroscopically examined and no instances of extensive corrosion were found. Overall, the in-vitro corrosion studies and the examination of retrieved prostheses predicted no exaggerated in-vivo corrosion due to the coupling of these cobalt and titanium alloys. 

Band L, Bencini A, Benelli C, Gatteschi D, Zanchini C (1982) Spectral-Structural Correlations in High-Spin Cobalt(II) Complexes. 52 37-86 Band L, Bertini I, Luchinat C (1990) The H NMR Parameters of Magnetically Coupled Dimers-The Fe2S2 Proteins as an Example. 72 113-136 Baran EJ, see MuUer A (1976) 26 81-139... 

The third reason for favoring a non-radical pathway is based on studies of a mutant version of the CFeSP. This mutant was generated by changing a cysteine residue to an alanine, which converts the 4Fe-4S cluster of the CFeSP into a 3Fe-4S cluster (14). This mutation causes the redox potential of the 3Fe-4S cluster to increase by about 500 mV. The mutant is incapable of coupling the reduction of the cobalt center to the oxidation of CO by CODH. Correspondingly, it is unable to participate in acetate synthesis from CH3-H4 folate, CO, and CoA unless chemical reductants are present. If mechanism 3 (discussed earlier) is correct, then the methyl transfer from the methylated corrinoid protein to CODH should be crippled. However, this reaction occurred at equal rates with the wild-type protein and the CFeSP variant. We feel that this result rules out the possibility of a radical methyl transfer mechanics and offers strong support for mechanism 1. 

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