Cobalt group metals, complexes with

Perchlorate ion complexes, 28 255-299 with cobalt group metals, 28 265-268 coordination types, 28 256-260 with copper group metals, 28 273-283 with early transition metals, 28 260-263 electronic spectra. 28 258-259 ESR spectra, 28 260 infrared and Raman spectra, 28 257-258 with iron group metals, 28 263-265 with lanthanides, 28 260-265, 287-288 magnetic susceptibility, 28 260 molar conductivities, 28 260 with nickel group metals. 28 268-273 X-ray crystal structure analysis, 28 256-257... 

Borovik s group studied the concept of cobalt complexes in a polymeric matrix as sensor in more detail. Four-coordinated Co(II) metal centers were incorporated into a porous methacrylate network by copolymerization of a styrene-substituted cobalt(II)(salen) complex with ethylene glycol dimethacrylate (see Figure 3) [19]. These complexes were specifically studied for their sensor capacity for NO [20]. 

Similarly, ra 5-cyclopropanes were obtained from alkenes, such as styrene and 2,5-dimethyl-hexa-2,4-diene, with relative yields > 90% when a diazoacetate bearing a bulky ester group was decomposed by a copper catalyst with bulky salicylaldimato ligands. Several metal complexes with bulky Cj-symmetrlc chiral chelating ligands are also suitable for this purpose, e.g. (metal/ligand type) copper/bis(4,5-dihydro-l,3-oxazol-2-yl)methane copper/ethyl-enediamine ruthenium(II)/l,6-bis(4,5-dihydro-l, 3-oxazol-2-yl)pyridine cobalt(III)/ salen. The same catalysts are also suited for enantioselective reactions vide infra). For the anti selectivity obtained with an osmium-porphyrin complex, see Section 1.2.1.2.4.2.6.3.1. 

One of the smallest naturally occurring peptides is camosine (jS-Ala-L-His) found in relatively large amounts in various animal tissues. Its exact function is not known. In the kidney an enzyme, carnosinase, hydrolyzes the peptide to its constituent amino acids. Also present in kidney is the highest in vivo concentration of cobalt, and Co complexes with carnosine are known to reversibly bind Oj. The inference is that carnosine (via its Co" complex) in kidney may control the O2 level. Further evidence is still needed for this conclusion. The extra methylene group in the -Ala moiety considerably alters the chelating properties of carnosine relative to other His-containing dipeptides (Chapter 20.2). This is particularly so with Cu" in aqueous solution where the major species is a dimer formed from the His moiety bridging the two metal centres. ... 

It is interesting to note the authors claim that the amount of ester incorporated onto the hydrogel was equal to the amount of template used during the formulation step. They also assumed that the ester occupied all of the imprinted cavities. The authors have used UV spectroscopy and ESR to characterize the structure of the complex prior to the removal of the metal center. Although the spectra were not shown, they reported studies which showed that cobalt formed a complex with 20, methacrylic acid (MAA), methacryloyl histidine (MA-His), and the template in the molar ratio 1 1 1 1 1. The authors interpretation of the spectra and explanation of the cobalt complexes with the polymer are confusing at best. The schematic diagrams that they report incorporate a hydroxyl group in the active site, which is not consistent with their spectral interpretations. 

Mordant dyes have hydroxy groups in their molecular stmcture that are capable of forming complexes with metals. Although a variety of metals such as iron, copper, aluminum, and cobalt have been used, chromium is most preferable as a mordant. Alizarin or Cl Mordant Red 11 [72 8-0] (1) (Cl 58000), the principal component of the natural dye obtained from madder root, is the most typical mordant dye (see Dyes, natural). The aluminum mordant of alizarin is a well-known dye by the name of Turkey Red and was used to dye cotton and wool with excellent fastness. However, as is the case with many other mordant dyes, it gave way to the vat or the azoic dyes, which are applied by much simpler dyeing procedures. 

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. 

There is also clear evidence of a change from predominantly class-a to class-b metal charactristics (p. 909) in passing down this group. Whereas cobalt(III) forms few complexes with the heavier donor atoms of Groups 15 and 16, rhodium(III), and more especially iridium (III), coordinate readily with P-, As- and S-donor ligands. Compounds with Se- and even Te- are also known. Thus infrared. X-ray and nmr studies show that, in complexes such as [Co(NH3)4(NCS)2]" ", the NCS acts as an A -donor ligand, whereas in [M(SCN)6] (M = Rh, Ir) it is an 5-donor. Likewise in the hexahalogeno complex anions, [MX ] ", cobalt forms only that with fluoride, whereas rhodium forms them with all the halides except iodide, and iridium forms them with all except fluoride. 

The performance of VASP for alloys and compounds has been illustrated at three examples The calculation of the properties of cobalt dislicide demonstrates that even for a transition-metal compound perfect agreement with all-electron calculations may be achieved at much lower computational effort, and that elastic and dynamic properties may be predicted accurately even for metallic systems with rather long-range interactions. Applications to surface-problems have been described at the example of the. 3C-SiC(100) surface. Surface physics and catalysis will be a. particularly important field for the application of VASP, recent work extends to processes as complex as the adsorption of thiopene molecules on the surface of transition-metal sulfides[55]. Finally, the efficiciency of VASP for studying complex melts has been illustrate for crystalline and molten Zintl-phases of alkali-group V alloys. 

Many carbonyl and carbonyl metallate complexes of the second and third row, in low oxidation states, are basic in nature and, for this reason, adequate intermediates for the formation of metal— metal bonds of a donor-acceptor nature. Furthermore, the structural similarity and isolobal relationship between the proton and group 11 cations has lead to the synthesis of a high number of cluster complexes with silver—metal bonds.1534"1535 Thus, silver(I) binds to ruthenium,15 1556 osmium,1557-1560 rhodium,1561,1562 iron,1563-1572 cobalt,1573 chromium, molybdenum, or tungsten,1574-1576 rhe-nium, niobium or tantalum, or nickel. Some examples are shown in Figure 17. 

There are few reports of oxidative addition to zerovalent transition metals under mild conditions three reports involving group 10 elements have appeared. Fischer and Burger reported the preparation of aTT -allylpalladium complex by the reaction of palladium sponge with allyl bromide(63). The Grignard-type addition of allyl halides to aldehydes has been carried out by reacting allylic halides with cobalt or nickel metal prepared by reduction of cobalt or nickel halides with manganese/iron alloy-thiourea(64). 

This small class of blue copper-complex dyes has made a significant contribution to the acid and reactive ranges in recent years (sections 5.4.2, 5.4-3 and 7.5.8). The essential chromogen is the bicyclic 1 1 chelated grouping illustrated (1.20). Trivalent metals such as chromium, nickel or cobalt will give tetracyclic 1 2 complexes with a central metal atom, analogous to conventional 1 2 metal-complex azo dyes. 

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