Type 11 G Dioxygen Complexes

In 1963 Vaska 164) discovered that the iridium complex Ir(PPh3)2C (CO) takes up molecular oxygen reversibly with 1 1 stoichiometry. This complex has since been shown to reversibly sorb (1 1) ethylene (755), carbon dioxide (765), F2C=CF2 and F3C—C=C—CF3 (767), as well as various other ligands (765). Ibers md La Placa (769) 

Infra-red absorption bands have been reported for a wide range of dioxygen complexes (77). In general, the only band observed for type 11(G) complexes is in the range 800—900 cm , which has been assigned to the 0-0 stretch (164). This assignment has been confirmed for 

Huber et al. 189) have investigated cocondensation (4.2—10 °K) reactions between Ni, Pd and Pt and molecular oxygen in pure O2 and Oj/Ar matrices. These reactions were studied by matrix isolation infra-red spectroscopy, including isotopic and diffusion controlled warm-up studies. They established that both M(02) and (0j)M(02) species were present. The 0-0 bond order suggested significant back-bonding, and this led them to reject the monodentate stmcture. Fig. 8 (b). 

They found that the order for the M—0 stretching modes (M—0 force constants) was (02)Pd(02) Pd(Oj) and (02)Ni(02) Ni(02), and since the 0-0 force constant increased as the M-0 force constant decreased, reversibility could not be equated with shorter 0—0 bond length. To test the proposed isosceles model they predicted the various absorptions that would be expected on the basis of the symmetrical structure (a) and unsymmetrical structure (c), Fig. 8. If the isotopic ratio of 0 0 is 1 1, then three bands would be expected for structure (a), with relative intensities 1 2 1, and four bands would be expected for structure (c), with relative intensities 1 1 1 1, the two oxygen atoms now being in different environments. These workers 189) then obtained the IR spectrum for the cocondensation product from the reaction between nickel and O2 (4.2—10°K), in isotopic ratio 0 =1 1, and found three bands with relative inten- 

Bayer and Schretzmann 25) came to the conclusion that reversible oxygenation is a characteristic property of group VIII metals. However, work has shown that the cadmium complex CdEt2 can take up dioxygen reversibly in the ratio 1 2 (Cd O2). But it was found that the oxygenated complex (II(P) or 11(G) orientation) can undergo spontaneous catalytic oxidation to form bis(ethylperoxy) cadmium  

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