Cobalt Oxygen Interaction

V. Pokhmurskii, S. Komiy, V. Kopylets Computer Simulation of Binary Platinum-Cobalt Nanoclusters Interaction with Oxygen, "Journal of Cluster Science", 22 (3), 449 58(2011). 

LCo(H20)6] ion, and bidentate /V-donor ligands such as cn, bipy and phen form octahedral cationic complexes [Co(L-L)3] , which are much more stable to oxidation than is the hexaammine [Co(NH3)6l . Acac yields the orange [Co(acac)2(H20)2] which has the tram octahedral structure and can be dehydrated to [Co(acac)2l which attains octahedral coordination by forming the tetrameric species shown in Fig. 26.3. This is comparable with the trimeric [Ni(acac>2]3 (p. 1157), like which it shows evidence of weak ferromagnetic interactions at very low temperatures. fCo(edta)(H20)] is ostensibly analogous to the 7-coordinate Mn and complexes with the same stoichiometry, but in fact the cobalt is only 6-coordinate, 1 of the oxygen atoms of the cdta being too far away from the cobalt (272 compared to 223 pm for the other edta donor atoms) to be considered as coordinated. 

In order to have more infoimation on the nature of the oxygen species active in partial and total oxidation we investigated the interaction of the hydrocarbons with the pre-oxidized surfaces of oxides where different types of surface oxygen species are formed. In particular we investigated p-type semiconductors like chromia, chromites and cobalt oxide C03O4. Moreover, we studied n-type metal oxides like FezOs, metal ferrites and CuObased catalysts. 

The presence of 0.3 wt.% Pd on Co-HFER (3 wt.%) catalyst results on a very important increase of low-temperature interaction of CH4 with N02, as a consequence of both the presence Pd species (Pd2+ and PdO) and the cobalt oxides redistribution (formation of Co oxo-cations and decrease of cobalt oxide). With bimetallic catalyst, under oxygen excess conditions, an increase of 30 % in the NOx conversion to N2 is attained. 

Acetylation occurs at the 2-position of allene systems (Scheme 8.14). The intermediate 7t-allyl complex breaks down via the nucleophilic displacement of the cobalt carbonyl group by the hydroxide ion to produce the hydroxyketone (7) [ 11 ]. An alternative oxygen-initiated radical decomposition of the complex cannot, however, be totally precluded. The formation of a second major product, the divinyl ketone (8), probably arises from direct interaction of the dicobalt octacarbonyl with the allene and does not require the basic conditions. 

Cobalt porphyrins have been some of the most studied catalysts for oxygen reduction, due in part to their strong interaction with molecular oxygen and the ease with which they catalyze the reduction at low potentials. Anson and coworkers [97] performed a study of the simplest of cobalt porphyrins, cobalt porphine, in the hope of gaining a baseline for the observed reactions of other porphyrins. Instead, they observed a very different process from most other monomeric cobalt porphyrins. 

As a last point, it should be mentioned that cobalt(II) salen (26) and cobalt(II) salophen (27) are known to interact with molecular oxygen in solution. Dioxygen forms a peroxo bridge between two cobalt centers, resulting in an often-undesired dicobalt(III) species that can attenuate the efficiency of electrogenerated cobalt(I) salen or cobalt(I) salophen for other reactions of interest, for example, the catalytic reduction of alkyl halides discussed in the following text. 

A point that seems to have been coming out of all of our work is that in interactions, especially oxidation-reduction reactions involving oxygenated species, we have to consider such condensations as this. I shouldn t be surprised if they were involved in a lot of the reactions involving simple metal ions which are hydrated. A recent article (2) states that bichromate also condenses with an aquo complex of cobalt with a much higher formation constant than that for CrSCV2 and with... 

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