Cobalt complexes reaction with oxygen

An additional study on the reaction of molecular oxygen with an NHC complex is depicted in Scheme 10.3 [13]. The tri-NHC cobalt complex 9 is obtained by reaction of T1MEN > 8 (TIMEN = tris[2-(3-alkylimidazol-2-ylidene)ethyl]amine) with... 

CoCl(PPh3)3], Reaction of [Co(TIMEN )]Cl 9 with oxygen in the presence of NaBPh leads to the formation of the peroxo-complex [Co(r -02)(TIMEN 5 )] BPh 10, which is a rare example of a side-on r -peroxo cobalt complex (the majority of Co-O -adducts are rj -O -complexes, i.e. end-on). The authors also showed that 10 is capable of converting molecular oxygen to benzoylchloride. 

Thiocarbamate (tc, RHNCSO-) is a monodentate ambidentate ligand, and both oxygen- and sulfur-bonded forms are known for the simple pentaamminecobalt(III) complexes. These undergo redox reactions with chromium(II) ion in water via attack at the remote O or S atom of the S- and O-bound isomers respectively, with a structural trans effect suggested to direct the facile electron transfer in the former.1045 A cobalt-promoted synthesis utilizing the residual nucleophilicity of the coordinated hydroxide in [Co(NH3)5(OH)]2+ in reaction with MeNCS in (MeO)3PO solvent leads to the O-bonded monothiocarbamate, which isomerizes by an intramolecular mechanism to the S-bound isomer in water.1046... 

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... 

Although no direct evidence was found in the cobalt-N-hydroxyethylethyl-enediamine reaction that an oxygen-cobalt addition complex was formed, it seems reasonable to postulate that such an intermediate is present in the reaction. An oxygen-cobalt complex intermediate appears to afford the most logical method of explaining the evidence that the oxidation of cobalt (II) to cobalt (III) occurs in conjunction with the oxidative cleavage of the carbon-carbon bond of the hydroxyethyl group and the formation of ethylenediamine. 

Hexaammineplatinum(IV) salts also undergo imine-forming reactions with acetylacetone (equation 49).172 A cobalt(III) acetylacetone complex can be formed as a result of intramolecular addition of cobalt-bound hydroxide ion to acetylacetone. The cobalt-bound oxygen atoms are retained in the new chelate ring (equation 50).173... 

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