Cobalt complexes oxygen-atom transfer

M s 1). Consideration of reaction (6) suggests that these reactions fail, despite the stability of the 0-P< >2 an< SO3 products, because the primary product cobalt species is an unstable cobalt(III)-radical complex, Co-(0 ) This, in turn, suggests that oxygen atom transfer could succeed if accompanied by elec-... 

Perhaps the most interesting of the inner-sphere pathways are those which result in the net transfer of an oxygen atom. The factors governing the viability of this pathway are still speculative. For cobalt-02 adducts, thermochemical considerations suggest that oxygen atom transfer should be accompanied by electron transfer in the reverse direction. Similarly, this pathway should be enhanced for MO2 complexes in which the metal... 

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... 

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