Dioxygen adducts

A dramatic discovery in this area was made in 1996 when a dicopper-dioxygen adduct was found to have two isomeric forms which featured either a side-on bridging unit Cu(/r ), ) -02)-Cu) " or a cyclic (Cu(/r-0)2Cu) " core depending on whether it was crystallized from CH2CI2 or thf, respectively. The two forms could be readily interconverted by reversible 0-0 bond cleavage and reformation, the 0-0 distance being 141 pm and 229 pm in the two isomers.The... 

The orange complex, though quite air stable in the solid state, forms an irreversible dioxygen adduct (IR i/(0—O) 845 cm-1) in solution within a few minutes. The complex likewise adds H2, HC1, HBr and, reversibly, CO. An adduct with MeNC is formed by a photochemical route ... 

The most versatile route involves the synthesis of the MeCN complex the weakly bound nitrite is readily replaced by a variety of anions. These generally react in a similar way to the chloride, IR data for these and their dioxygen adducts are given in Table 2.9 [129]. 

Proniewicz LM, Odo J, Goral J, Chang CK, Nakamoto K. 1989. Resonance Raman spectra of dioxygen adducts of pillared cobalt cofacial diporphyrins. J Am Chem Soc 111 2105. 

Proniewicz LM, Paeng IR, Nakamoto K. 1991. Resonance raman spectra of two isomeric dioxygen adducts of iron(II) porphyrins and rr-cation radical and nonradical oxoferryl porphyrins produced in dioxygen matrixes Simultaneous observation of more than seven oxygen isotope sensitive bands J Am Chem Soc 113 3294. 

A full discussion of the reactions of molecular oxygen involved in dioxygen adducts would require a separate review. Moreover, the reactions of co-ordinated molecular oxygen are discussed elsewhere l-8) dioxygen adducts of biological systems (7) and synthetic group VIII metal complexes 1,3) being of particular interest. 

Further to section III(C), we shall see that type I dioxygen complexes can be formed in solution via intermediates of a type 11(F) structure. Consequently, sections IV( ) and IV(F) will tend to overlap in places. The dioxygen adducts of some new synthetic metal porphyrins belong to the 11(F) classification. However, a discussion of the dioxygen adducts of naturally occurring and synthetic metal porphyrins is postponed until section V. 

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 ... 

Much work has been devoted to the study of Schiff base complexes, in particular M(salen), where M = metal, has been the subject of extensive work 114). The early work by Calvin et al. (section 111(A)) suggested that the 2 1 (M O2) dioxygen adduct, type I, formed by Co(salen) in the solid state, contains a peroxo linkage. An X-ray analysis 115, 116) of the complex (Co Salen)202(DMF)2 supports this hypothesis see Fig. 5 for the pertinent results of this study. 

We have seen, in the previous section (and section III.A), that cobalt (Salen) and its active derivatives normally form diamagnetic peroxo type I dioxygen adducts. However, a pyridine solution of Co(3-methoxy Salen) has been shown 137) to take up dioxygen with 1 1 (Co O2) stoichiometry it was found 137) that there was no significant IR absorption band, attributable to the 0—0 stretch, for the oxygenated complex, and this suggested that the dioxygen is symmetrically bonded in an unidentate manner,... 

It is clear from the ESR studies that have been reported that the majority of workers favour the Co(III)-0 formulation for most mononuclear type II(/ ) dioxygen adducts. 

An X-ray photoelectron spectroscopic study (132) of some cobalt(II) Schiff base complexes and their dioxygen adducts finds that the cobalt core electron binding energies in... 

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