Group cobalt containing

Vitamin B12 (Fig. 1) is defined as a group of cobalt-containing conoids known as cobalamins. The common features of the vitamers are a corrin ting (four reduced pyrrole rings) with cobalt as the central atom, a nucleotide-like compound and a variable ligand. Vitamin B12 is exceptional in as far as it is the only vitamin containing a metal-ion. The vitamers present in biological systems are hydroxo-, aquo-, methyl-, and 5 -deoxyadenosylcobalamin. 

A component of the ribotide reductase complex of enzymes, protein Ba, has been shown to contain two non-heme iron atoms per mole (77). This enzyme plays a vital, albeit indirect, role in the synthesis of DNA. Curiously, the lactic acid bacteria do not employ iron for the reduction of the 2 hydroxyl group of ribonucleotides. In these organisms this role has been assumed by the cobalt-containing vitamin Bi2 coenzyme (18). The mechanism of the reaction has been studied and has been shown to procede with retention of configuration (19). 

The name vitamin B12 indicates a group of cobalt-containing corrinoids, also described as cobala-mins. Hydroxycobalamin (HOCbl), adenosylcobalamin (AdoCbl), and methylcobalamin (MeCbl) are the natural occurring forms. Instead, cyanocobalamin (Figure 19.20) is the commercially available form used for supplements and food fortification, thanks to its greater relative stability. Occasionally, sulfitocobalmin can occur in processed foods. Vitamin B,2 functions as a coenzyme and it is linked to human growth, cell development, and is involved in metabolism of certain amino acids. Vitamin B12 is present mainly in meat and diary foods, therefore a deficiency can occur in... 

A second group of ribonucleotide reductases (Class II), found in many bacteria, depend upon the cobalt-containing vitamin B12 coenzyme which is discussed in Section B. These enzymes are monomeric or homodimeric proteins of about the size of the larger a subunits of the Class I enzymes. The radical generating center is the 5 -deoxyadenosyl coenzyme.350 364 365... 

It is apparent from most of the examples previously described that the most common formal oxidation state found for the Group 14 element is E(IV) (E = Ge, Sn, Pb). Relatively few examples of divalent germanium, tin, or lead complexes have been described, and of these, many are not well characterized. Cobalt-containing compounds are no exception in this regard and there appears to be only one report in the literature that describes a species of this type, viz. [Ge Co(CO)4 2], 67, although the precise structure of this complex is unknown (77). Two main synthetic routes are described, Eqs. (4) and (S), the starting complex in the latter reaction being... 

Several macrocyclic ligands are shown in Figure 2. The porphyrin and corrin ring systems are well known, the latter for the cobalt-containing vitamin Bi2 coenzymes. Of more recent interest are the hydroporphyrins. Siroheme (an isobacteriochlorin) is the prosthetic group of the sulfite and nitrite reductases which catalyze the six-electron reductions of sulfite and nitrite to H2S and NH3 respectively. The demetallated form of siroheme, sirohydrochlorin, is an intermediate in the biosynthesis of vitamin Bi2, and so links the porphyrin and corrin macrocycles. Factor 430 is a tetrahydroporphyrin, and as its nickel complex is the prosthetic group of methyl coenzyme M reductase. F430 shows structural similarities to both siroheme and corrin. 

Vitamin B12 is a biologically active corrinoid, a group of cobalt-containing compounds with macrocyclic pyrrol rings. Vitamin B12 functions as a cofactor for two enzymes, methionine synthase and L-methylmalonyl coenzyme A (CoA) mutase. Methionine synthase requires methylcobalamin for the methyl transfer from methyltetrahydrofolate to homocysteine to form methionine tetrahy-drofolate. L-methylmalonyl-CoA mutase requires adenosylcobalamin to convert L-methylmalonyl-CoA to succinyl-CoA in an isomerization reaction. An inadequate supply of vitamin B12 results in neuropathy, megaloblastic anemia, and gastrointestinal symptoms (Baik and Russell, 1999). 

They noted that in dimethoxyethane or in iso-octane (path a), the major product was dicarbonylcyclopentadienylcobalt (2) which must arise as a result of a retro Diels-Alder reaction of the norbornadiene (which would lead to the formation of acetylene and cyclopentadiene). When the solvent was changed to an aromatic hydrocarbon such as benzene or toluene (path b), the major cobalt-containing product was shown to be a complex derived from Co4(CO)i2, with three CO ligands on an apical cobalt being replaced by a molecule of the aromatic solvent (3). The group noted that they were also obtaining hydrocarbon and ketonic products derived from norbornadiene, acetylene and carbon monoxide .1,2... 

Figure 3 Schematic representation of a cobalt-containing NO sensor by Borovik s group.

The group of metals forming low-stability or unstable nitrides includes Mn, Fe, Co, Ni, Tc and Re. As in the case of iron a clear structural sensitivity was found for rhenium but the role of promoters remains the subject of discussion. There are also indications of structure sensitivity for cobalt and nickel. It was attempted to improve the activity of the classical magnetite catalyst by alloying with nickel or cobalt. The only commercial catalyst is a cobalt containing magnetite [392],... 

Complexes of cobalt containing PCF3 groups have been prepared independently by two groups, (116, 117) and parameters reported are shown with structures [220] to [224]. The P-CF3 coupling constant is increased in each case compared with that in the free ligand, as expected. Compound [222] appears from the spectra to be a mixture of isomers a and b the separation of the second order doublet for the major isomer is 88 Hz. The spectrum of [223] is also second order, with a major doublet separation of 68 Hz. Compound [224] shows inequivalent CF3 groups attached to phosphorus, and a bent Co-Co bond is invoked to account for this. (117)... 

Part of the cobalt-containing coenzyme B12 is shown in Fig. Id. The group X is variable X=CH3... 

Tang and co-workers have also prepared cobalt-containing hyperbranched polymers by the reaction of cobalt complexes with a preformed hyperbranched polymer 274 containing acetylene groups.321 The percent of cobalt incorporated into the polymers ranged from 27.8 to 36.7 wt %, and upon high temperature pyrolysis, the polymers formed ceramics with magnetic properties. 

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