Metal -dioxygen complexes

Dioxygen-metal complexes in which there is a 1 1 stoichiometry of 02. M are of two main types, usually designated la (or superoxo) and Ila (or... 

Table 14.5 Summary of properties of known dioxygen-metal complexes ...

Dioxygen metal complexes towards a unified view. L. Vaska, Acc. Chem. Res., 1976, 9, 175-183... 

It is important to form a stable 1 1 dioxygen-metal complex, because oxyhemoglobin and oxymyoglobin are 1 1 dioxygen-iron complexes which can reversibly... 

A polymer ligand might be expected to protect the dioxygen-metal complex against autoxidation in much the same way as the globin protein does. In this chapter, we describe how polymer-metal complexes react with molecular oxygen and introduce attempts to construct synthetic oxygen carriers. 

In general, the oxidation of primary alcohols to carboxylic acids using T)2-dioxygen metal complexes is rare. To our knowledge, only one report (134) communicates such a process. 

Coordination modes of dioxygen metal complexes (a) -superoxo,... 

The stretching frequencies attributed to the 0-0 vibration are closely related to the structural type. Type I complexes show 0-0 stretching vibrations around 1125 cm-1 and type II around 860 cm-1. This sharp difference enables the O-O stretching frequency as measured by infrared or Raman spectroscopy to be used for structure type classification. Table 16.2.2 lists the structural data of dioxygen metal complexes. 

Dioxygen-metal complexes towards a unified view (L. Vaska, Accounts Chem. Res., 1976, 9, 1975). Synthetic oxygen carriers of biological interest (F. Basolo, B. M. Hoffman, and J. A. Ibers, Accounts Chem. Res., 1975,8, 384). 

Vaska L. Dioxygen-metal complexes-toward a unified view. Acc Chem Res 1976 9 175-83. 

Scheme 4.13 Possible pathways to transition metal peroxocarbonates from dioxygen-metal-complexes and CO2 (adapted from [73])...

The reaction, known for a long time, is the one implying the addition of CO2 to a dioxygen-metal-complex [69-72]. Nevertheless, very little was known about the reaction mechanism. Only recently have smdies been carried out to shed light on the reaction of dioxygen complexes with CO2 [73-75] or of carbon dioxide complexes with O2 [76]. Two ways are possible, which imply the 0-0 (Scheme 4.13, routes la, 2a) or M-O bond opening (Scheme 4.13, routes lb, 2b) with subsequent CO2 insertion and ring closure to afford the peroxocarbonate structure. 

L. Vaska - Dioxygen-Metal Complexes Towards a Unified View,... 

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