Cobalt zinc derivative

The ability of cobalt(II), nickel(II), and copper(II) to exhibit a greater tendency than Zn(II) towards bidentate coordination is further illustrated by structural comparisons within a series of bridging carbonate complexes (188). For example, of the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu, Zn), only the zinc derivative does not exhibit bidentate coordination at both metal centers (151,153). Furthermore, the carbonate ligand in the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu) also exhibits varying degrees of asymmetry that closely parallel the series of nitrate complexes described earlier (Fig. 47 and Table IX). 

Unfortunately, crystals of X-ray diffraction quality for the above cobalt and zinc derivatives could not be obtained. Thus, tentative assignments of structure were made on the basis of mass spectrometric analysis. Such studies were consistent with the apparent complexation of only one metal atom by the sapphyrin core. They also revealed a parent ion for each of these complexes that was considered most in accord with the symmetrical structures represented by 5,83 and 5.84 (Figure 5.5.1). In other words, based on these analyses. Woodward and coworkers proposed cobalt(II) and zinc(II) sapphyrin complexes wherein only four of the five possible nitrogen centers interacted with the metal center, and only two of the three possible NH protons became lost upon complexation. ... 

This procedure consists of refluxing an acetone solution of the /3-keto imine with a freshly prepared metal hydroxide. The product precipitates from solution upon cooling or is obtained by dilution of the acetone solution with water. The method has been used to prepare the copper(II), nickel(II), and cobalt(II) derivatives of a variety of /3-keto imines, - but attempts to prepare zinc and cadmium derivatives were not successful. The advantages of this procedure have been described previously. On occasion, the chelate compound may precipitate during the reaction... 

Most catalysts that have been mentioned so far are mononuclear. The few binuclear compounds utilized Co2(CO)8 or phosphinesubstituted derivatives) did not give evidence of any unusual type of binuclear catalysis. However, new products could result with catalysts producing two active centers in close vicinity which would not dissociate in the course of the reaction. The expected difference between mononuclear and binuclear catalysis is shown in the accompanying diagram (52). A series of metal salts of cobalt carbonyl hydride of composition M[Co(C0)4]n (M=Zn, Cd, Hg, n = 2 M = In, = 3) were tested as potential binuclear catalysts. The complex salts are relatively easily accessible Zn[Co(CO)4]2, for instance, may be prepared from cobalt carbonyl, metallic zinc, and CO (at 3000 psi initial pressure) using toluene as the solvent and a temperature of 200°. The compound may also be synthesized directly from metallic cobalt, zinc, and CO... 

TETRAKIS(BENZENETHIOLATO)METALLATE(2-) COMPLEXES, [M(SPh)4]2, OF MANGANESE, IRON, COBALT, ZINC, AND CADMIUM AND DERIVATIVES OF THE [Fe(SPh)4]2 COMPLEX... 

The complex cation in [Fe FB(ONCH-CsH3N)3P IBFJ,CHjClj contains a rigid, sexidentate ligand, designed specially to force a trigonal-prismatic co-ordination geometry on first-row transition metals. It does it successfully with the nickel(ii) ion, and probably also in the isomorphous zinc(ii) and cobalt(ii) derivatives, but in the case of the iron(ii) cation... 

A variety of cobalt carbonyl derivatives have been obtained in which the cobalt atom is o-bonded to an element other than carbon. These have been obtained both by wet methods involving metathesis of a solution of [Co(CO)4] with an appropriate derivative of the element to be bonded to cobalt and by dry methods involving high-pressure reactions of carbon monoxide with a mixture of cobalt metal or one of its compounds and an appropriate derivative of the other element. Thus, treatment of aqueous solutions of [Co(CO)4] with silver nitrate or mercury(II) cyanide gave the derivatives AgCo(CO)4 or Hg[Co(CO)4], respectively (220). The mercury derivative can also be prepared by the dry method, involving treatment of a mixture of mercury(II) bromide and cobalt metal with 200 atm of carbon monoxide at 150° C (247). The silver derivative AgCo(CO)4 could not be prepared by the dry method (247). The yellow zinc and cadmium derivatives M[Co(CO)4]2 (M = Zn or Cd) can be obtained by treatment of cobalt(II) bromide, cobalt metal, or dicobalt octacarbonyl with zinc or cadmium metal in the presence of carbon monoxide under pressure (247). 

Despite the weak basicity of isoxazoles, complexes of the parent methyl and phenyl derivatives with numerous metal ions such as copper, zinc, cobalt, etc. have been described (79AHC(25) 147). Many transition metal cations form complexes with Imidazoles the coordination number is four to six (70AHC(12)103). The chemistry of pyrazole complexes has been especially well studied and coordination compounds are known with thlazoles and 1,2,4-triazoles. Tetrazole anions also form good ligands for heavy metals (77AHC(21)323). 

Analogously, pyrazolyl-aluminate and -indate ligands have been prepared <75JCS(D)749) and their chelating properties evaluated with cobalt, nickel, copper and zinc. Gallyl derivatives of pyrazoles and indazoles have been extensively studied by Storr and Trotter e.g. 75CJC2944) who determined several X-ray structures of these compounds. These derivatives exist in the solid state as dimers, such as (212) and (288). A NMR study in acetone solution showed the existence of a slow equilibrium between the dimer (212) and two identical tautomers (289) and (290) (Section 4.04.1.5.1) (81JOM(215)157). 

The sotrace elements, such as boron, cobalt, iron,copper, zinc, manganese, chromium, molybdenum and still others may also be used to advantage. Generally, these trace elements occur in sufficient quantities in the carbonaceous and nitrogenous constituents of the medium, particularly if derived from natural sources, or in the tap water, and the addition of further quantities of these trace elements may consequently be unnecessary. 

The most commonly used stabilizers are barium, cadmium, zinc, calcium and cobalt salts of stearic acid phosphorous acid esters epoxy compounds and phenol derivatives. Using stabilizers can improve the heat and UV light resistance of the polymer blends, but these are only two aspects. The processing temperature, time, and the blending equipment also have effects on the stability of the products. The same raw materials and compositions with different blending methods resulted in products with different heat stabilities. Therefore, a thorough search for the optimal processing conditions must be done in conjunction with a search for the best composition to get the best results. 

Compounds 139 are tris(oximehydrazone) derivatives with an iron(ll) ion in the center of the cavity [230]. Compound 140 (Fig. 38) has been known for 30 years [231, 232] and was prepared from a tris(2-aldoximo-6-pyridyl)phos-phine that is capped by a BF unit to encapsulate cobalt(ll), zinc(ll), nickel(ll), and iron(II). All four macrocyclic complexes were characterized later by a comparative X-ray crystallographic study [233-236]. 

Treatment of the 1,2-oxazines 52 with carbon monoxide at 1000 psi in the presence of cobalt carbonyl brings about insertion of carbon monoxide to form the 1,3-oxazepines S3 <96TL2713>. A convenient route to P-lactams fused to oxepines is made available by alkene metathesis. Thus reaction of 4-acetoxyazetidin-2-one with ally alcohol in the presence of zinc acetate, followed by iV-allylation of the nitrogen affords the derivative 54 which cyclises by RCM to form the oxazepinone 55 <96CC2231>. The same communication describes a similar synthesis of 1,3-dioxepines. 

IH of alkynylamines has been performed with a variety of catalytic systems based on palladium [274-281], cobalt, rhodium, iridium, ruthenium, platinum, copper, silver, zinc, cadmium, mercury [279-281], nickel [279-282], gold [279-281, 283], and molybdenum [284] derivatives. 

Bied-Charreton (63) showed by XH NMR spectroscopy that a zinc porphyrin bearing a primary amino group attached via a flexible spacer to the meta position of a /neso-phenyl ring spontaneously dimerizes in solution via NH Zn coordination. The corresponding ortho derivative shows an equilibrium between the dimeric form and the intramolecu-larly coordinated monomer. ESR spectroscopy was used to demonstrate the same behavior in the corresponding cobalt porphyrin (64). 

The introduction of redox activity through a Co11 center in place of redox-inactive Zn11 can be revealing. Carboxypeptidase B (another Zn enzyme) and its Co-substituted derivative were oxidized by the active-site-selective m-chloroperbenzoic acid.1209 In the Co-substituted oxidized (Co111) enzyme there was a decrease in both the peptidase and the esterase activities, whereas in the zinc enzyme only the peptidase activity decreased. Oxidation of the native enzyme resulted in modification of a methionine residue instead. These studies indicate that the two metal ions impose different structural and functional properties on the active site, leading to differing reactivities of specific amino acid residues. Replacement of zinc(II) in the methyltransferase enzyme MT2-A by cobalt(II) yields an enzyme with enhanced activity, where spectroscopy also indicates coordination by two thiolates and two histidines, supported by EXAFS analysis of the zinc coordination sphere.1210... 

Low-valent cobalt pyridine complexes, electrogenerated from CoCl2 in DMF containing pyridine and associated with a sacrificial zinc anode, are also able to activate aryl halides to form arylzinc halides.223 This electrocatalytic system has also been applied to the addition of aryl bromides containing an electron-withdrawing group onto activated alkenes224 and to the synthesis of 4-phenylquinoline derivatives from phenyl halides and 4-chloroquinoline.225 Since the use of iron as anode appeared necessary, the role of iron ions in the catalytic system remains to be elucidated. 

Interesting results were reported with dithiocarbamates derived from diamines. Thus, a series of dinuclear zinc(II), cobalt(II), and nickel(II) dithiocarbamate ditopic macrocyclic receptors containing various spacer groups of different sizes has been reported.412,413,414 Spectroscopic investigations and... 

The metal hydroxides that dissolve in an excess of aqueous NH3 to form ammine complexes are derived from the twelve metals of the cobalt, nickel, copper and zinc families. Therefore, when excess NH3 is added ... 

Recently, the high inhibitory efficiency of metalloporphyrins has been shown in lipid peroxidation of rat brain homogenates [346]. It was found that manganese and cobalt porphyrins were very effective inhibitors of lipid peroxidation while iron and especially zinc porphyrins had very weak inhibitory activity, if any. For example, /50 values were equal to 21, 29, 212, 946 pmol 1 1 for CoTBAP, MnTBAP, FeTBAP, and ZnTBAP, respectively, where TBAP is 5,10,15,20-tetrakis [4-carboxyphenyl]porphyrin similar values were obtained for other porphyrin derivatives. 

Unexpected uniformities observed in the impact-sensitivities of a group of 22 amminecobalt oxosalts are related to kinetic factors during the initiation process [6], A series of ammine derivatives of cadmium, cobalt, copper, mercury, nickel, platinum and zinc with (mainly) iodate anions was prepared and evaluated as explosives [7], Earlier, ammine and hydrazine derivatives of cadmium, cobalt, copper and nickel with chlorate or perchlorate anions had been evaluated as detonators. Dihydrazinecopper(II) chlorate had exploded when dried at ambient temperature [8],... 

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