Oxygen with organometallic

SINGLET OXYGEN DIMOL-SENSITIZED LUMINESCENCE AND REACTIONS OF SINGLET OXYGEN WITH ORGANOMETALLICS... 

Reactions other than Lewis acid-base associations/dissociations are frequently observed wit donor molecules, leading notably to solvolysis, oxygen or sulfur abstraction, insertion reaction and carbon-carbon coupling reactions. The tendency to form metal-element multiple bonds i remarkable in this respect the activation of dinitrogen by tantalum or niobium is unique. Th formation and chemistry of constrained reactive metallacycles open another promisin fast-developing area, on the frontier with organometallic chemistry. 

Not only alkenes and arenes but also other types of electron-rich compound can be oxidized by oxygen. Most organometallic reagents react with air, whereby either alkanes are formed by dimerization of the metal-bound alkyl groups (cuprates often react this way [80]) or peroxides or alcohols are formed [81, 82]. The alcohols result from disproportionation or reduction of the peroxides. Similarly, enolates, metalated nitriles, phenolates, enamines, and related compounds with nucleophilic carbon can react with oxygen by intermediate formation of carbon-centered radicals to yield dimers (Section 5.4.6 [83, 84]), peroxides, or alcohols. The oxidation of many organic compounds by air will, therefore, often proceed faster in the presence of bases (Scheme 3.21). 

In any case, the relative photochemical stability of both Ceo und C70 and their low fluorescence yields make these compounds particularly useful as photosensitizers. For example, they have been used to prepare some novel oxygen-metal adducts by reaction of singlet oxygen with certain organometallic complexes [51]. 

Fig. 4. Porosil structures (oxygen atoms omitted) that have so far been synthesized with organometallic complexes as SDAs a) NON topology, b) AST topology, c) DOH topology, d) ZSM-48, e) UTD-1.

However, to the best of our knowledge, there are no repuitS c/i hemical reaction of single oxygen with metal centers in organometallic complexes. 

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