Dioxygen complexes bonding

Figure 3.18 Metal-dioxygen bonding in platinum-dioxygen complexes.

Bond lengths (Continued) carbonyl complexes dioxygen complexes disulphur complexes dithiocarbamates Mlerene complexes halide complexes halides... 

The structure and reactivity of dioxygen complexes of the transition metals, M. H. Gubelmann and A. F. Williams, Struct. Bonding (Berlin), 1983,55,1-65 (529). 

Continuing their efforts with similar ligands, they prepared a thermally sensitive crystal of a bis(/i-qxo)dicopper(II I) compound (3).28 Average Cu O bond distance and Cu-Cu distance are 1.806 A and 2.743 A, respectively. Spectroscopic and kinetic parameters for this compound were also investigated. They also studied the reactivity properties of the copper-dioxygen complexes.25... 

The crystal structure of the dioxygen complex Tp V(0)(02)(L) has been determined, and revealed a side-on bonded O2 ligand. Based on the O - O distance of 1.379(6) A and vo-o of 960 cm it was formulated as a V(V) peroxo complex, even though these values are on the borderline between the peroxo and superoxo designations. The mechanism of this reaction is curious. Reaction with 02 showed incorporation of solely in the O2 ligand and not in the 0x0 groups. It appears that the O2 binding step must be preceded by a disproportionation (2 V(IV) V(III) + V(V)) followed by reaction of V(III) with O2. 

Unlike Au+(02), which was green,224 both Ag+(02) and Ag+(04) were colourless, although weak absorptions at 275 and 290 nm respectively were observed in their UV spectra. Ag+(02) was formulated as a side-on -bonded superoxo molecular species and this was supported by IR spectra. Ag+(C>4) was described as a tetraoxygen species rather than a bis(dioxygen) complex. Neither copper nor gold gave a secondary reaction to produce a related M+(04-) complex. 

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