Cobalt-containing systems

In the nickel—carbon and cobalt—carbon systems, the nickel carbide (3 1) [12012-02-1], Ni C, and cobalt carbide (3 1) [12011-59-5] C03C, are isomorphous with Fe C and exist only at low temperatures. The manganese—carbon system contains manganese carbide (3 1) [12121 -90-3] Mn C, isomorphous with Fe C, and manganese carbide (23 6) [12266-65-8] isomorphous with chromium carbide (23 6) [12105-81 -6] These... 

Phase composition changes as a function of temperature are similar to these that were observed for the lithium-containing system (see Fig. 21), except that individual stable ammonium-cobalt-oxyfluoroniobate occurs prior to the formation of CoNbOF5 (Fig.21, curve 4). It is assumed that the composition of this intermediate phase, formed at 330-350°C, is (NH CoNbOFy [129]. Complete removal of ammonium occurs at about 400°C (Fig. 21, curve 5) and leads to the formation of CoNbOFs. The compound is defined as practically isotropic rose-colored ciystals with a refractive index of N = 1.500. The... 

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. 

The effects of manganese on the cobalt/bromide-catalyzed autoxidation of alkylaromatics are summarized in Figure 17. The use of the Mn/Co/Br system allows for higher reaction temperatures and lower catalyst concentrations than the bromide-free processes. The only disavantage is the corrosive nature of the bromide-containing system which necessitates the use of titanium-lined reactors. 

With sp bond angles calculated to be around 162°, macrocycle 131 would be highly strained and was therefore expected to be quite reactive [79]. The octa-cobalt complex 132, on the other hand, should be readily isolable. Indeed, 132 was prepared easily from 133 in five steps, and was isolated as stable, deep maroon crystals (Scheme 30). All spectroscopic data supported formation of the strain-free dimeric structure. Unfortunately, all attempts to liberate 132 from the cobalt units led only to insoluble materials. Diederich et al. observed similar problems when trying to prepare the cyclocarbons [5c]. Whether the failure to prepare these two classes of macrocycles is due to the extreme reactivity of the distorted polyyne moiety or to the lack of a viable synthetic route is not certain. Thus, isolation and characterization of smaller bent hexatriyne- and octatetrayne-containing systems is an important goal that should help answer these questions. 

As an appropriate concluding section in this wide-ranging review of oxygen activation by cobalt-, rhodium-, and iridium-containing systems, it has been reported (233) that molten sodium meta-phosphate (NaP03), at 850°C, reacts with dioxygen to produce the superoxide... 

In the case of amino acid ester and amide complexes, the intramolecular hydrolysis reaction was not observed directly, but was deduced from the results of lsO tracer studies. However, recently the cis-hydroxo and cis-aqua complexes derived from the bis(ethylenediamine)cobalt(III) system, containing glycinamide, glycylglycine and isopropylglycylglycinate, have been isolated and their subsequent cyclization studied over the pH range 0-14.160,161... 

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. 

Some promise is offered by the application of PCMU to power conversion devices [137], Thus polymeric cobalt-containing porphyrins can be used for photochemical power storage in a norbornadiene-quadricyclane system [138]. 

In metal-containing systems, synthons involving coordinated water or am-mine ligands are possible. For example, hydrogen bonding between coordinated water and pyridine oxide ligands in a R2(8) motif has been observed to link cobalt 4,4 -bipyridine dioxide coordination polymers into sheets [60]. 

The polymer cobalt containing prophyrins (32), (33) were used in the photochemical energy storage system norbomadiene-quadricyclane (Eq. IS) This system for storage of solar energy is useful because of the high AH value between the two valence isomers on one side and the low price for the starting material (norbornadiene) on the other side. 

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