Dioxygen ions

The coordinately unsaturated [M(bpy)]+ ions of Co, Ni, and Cu were also reacted with 02. The Co and Ni complexes formed the dioxygen ion but the Cu complex was unreactive. 

In most oxidation processes dioxygen ions are considered undesirable, but they appear to be essential in the oxidation of ethylene to ethylene oxide (oxirane). 

Clearly other combinations of logical and illogical synthons could be used to make 1,4-dioxygenated compounds. How could you use cyanide ion (as the CO2H synthon) to make a y-keto acid such as... 

T.G. Spiro (ed.). Metal Ion Activation of Dioxygen, Wiley-Interscience, New York, 1980, 247 pp. 

The synthesis of precursors for the generation of the enantiomerically pure mono- and trans-dioxygenated /V-acyliminium ions of type 335,36 and 643 is achieved by reduction of the corresponding optically active imides. 

In summary, the cooperative behavior of the two metal ions determines the dioxygen chemistry of group 2 bis-Co porphyrins and certain flexible group 1 analogs (e.g., a... 

Taube H. 1986. Interaction of dioxygen species and metal ions—Equilibrium aspects. Prog Inorg Chem 34 607. 

A large number of type 1 dioxygen adducts are reported in the literature (25, 76, 80). The vast majority of metal complexes which take up dioxygen to form type I adducts contain cobalt(ll) as the metal ion. Ochiai (81) considered the hypothetical reactions ... 

Anson and co-workers have shown that two Co ions were not necessary for four-electron 02 reduction.266 The mew-substituted complex porphyrin Co(TPyP) (42) complex bears four active pyridyl donors which readily react with four equivalents of [Ru(NH3)5(OH2)]2+ to produce the tetra-ruthenated derivative. The four Ru centers are sufficiently remote that their RuIII/n potentials coincide. Under steady state conditions [Co(TPyP)] Ru(NH3)5 4]8+ (43) adsorbed onto a pyrolytic graphite working electrode catalyzes the reduction of dioxygen (Figure 6). 

Dioxygen and its ions can bind in mononuclear and dinuclear structures in a number of ways,962 as illustrated in Scheme 1. The typical reaction of dioxygen with Co compounds involves a number of these binding forms, outlined in Scheme 2. Mononuclear Co111—peroxo complexes are relatively rare, but yellow trigonal bipyramidal complexes [Co(02)L2]+ (L = chelating phosphines dppe or dppp) have been characterized structurally where the 022 is bonded to the Co in the side-on r]2 form (Co—O 1.858(7) 1.881(4) A), with O—O stretching frequencies ( 870 cm-1) consistent with Coin-peroxo speciation.963... 

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