Metal oxygen atom transfer

Keywords Organometallics Dioxygen Early transition metals Oxygen atom transfer... 

Among the transfer and exchange of non-metals, the reactions of atomic oxygen, O, at low potential are unusual in that transport is not required. H20 carries O everywhere but it is not by itself active in O-incorporation into carbon frameworks. It is observed that fixed Mo (W) coenzymes have always been used as catalysts in the oxygen atom transfer from H20 to aldehydes reversibly. 

Perhaps the most interesting of the inner-sphere pathways are those which result in the net transfer of an oxygen atom. The factors governing the viability of this pathway are still speculative. For cobalt-02 adducts, thermochemical considerations suggest that oxygen atom transfer should be accompanied by electron transfer in the reverse direction. Similarly, this pathway should be enhanced for MO2 complexes in which the metal... 

These PVP polymers provide a "proximal effect" without addition of free pyridine in the reaction mixture. Different studies have shown that only one pyridine per manganese catalyst is sufficient to enhance the rate of the catalytic oxygen atom transfer from the high-valent metal-oxo species to the organic substrate. The advantage of PVP polymer over a cationic Amberlite resin (see Scheme II for structures) have been recently illustrated in the modeling of ligninase (11). 

The facile activation of dioxygen by these simple organometalHc complexes generates high-valent (V(V), Cr(V)) metal 0x0 complexes, which may undergo oxygen atom transfer reaction with organic substrates, and thus serve as catalysts for aerobic oxidations (Sect. 3.3). 

The formation of methylperoxy intermediates—i.e., the product of a formal insertion of O2 into the metal-methyl bond—was substantiated by the observation of epoxidation of allylic alkoxides (Scheme 6), in analogy to the proposed mechanism for the Sharpless epoxidation utilizing tert-butylhydroperoxide (TBHP). A similar oxygen atom transfer from a coordinated alkylperoxide to olefin was also postulated for the epoxidation of olefins with TBHP catalyzed by Cp Mo(0)2Cl [31]. The use of organomolybdenum oxides in olefin epoxidafion cafalysis (albeit not with O2) has recently been reviewed [32]. 

Intermolecular oxygen atom transfer from a metal complex to an organic substrate is an archetypical reaction step in oxidation catalysis. As the transformation of O2 into metal 0x0 groups by oxidative addition is a well-precedented process (Sect. 2.2), its combination with transfer of the oxygen atom to an oxidizable substrate ( S ) constitutes a catalytic cycle for aerobic oxidations (Eq. 21). Examples of such cycles exist in organometallic chemistry, by virtue of 0x0 complexes with carbon-based ancillary hgands. 

Oxidation Catalyzed by Metalloporphyrins. Much attention has been devoted to the metal-catalyzed oxidation of unactivated C—H bonds in the homogeneous phase. The aim of these studies is to elucidate the molecular mechanism of enzyme-catalyzed oxygen atom transfer reactions. Additionally, such studies may eventually allow the development of simple catalytic systems useful in functionalization of organic compounds, especially in the oxidation of hydrocarbons. These methods should display high efficiency and specificity under mild conditions characteristic of enzymatic oxidations. 

The special case of metal-mediated stoichiometric electrophilic oxygen atom transfer to aromatic ligands will be discussed in more detail in the next chapter. Suffice it to say here, that numerous examples of transition metal-mediated (particularly copper and iron) oxygen atom transfer are known, although many of these processes are catalytic. 

The discovery of the ds and d10 metal ir-bonded dioxygen complexes (formally d6- and d8-peroxide systems), and the accompanying chemistry exemplified in Scheme 1, showed the possibility of attaining net oxygen-atom transfer to both inorganic and organic substrates. 

Transition-metal oxides are useful oxidizing reagents for organic molecules and often participate in oxygen-atom transfer reactions [21]. A prototypical example is CH3Re03 (MTO), which serves as a versatile reagent for stoi-... 

Many compounds have been synthesized, characterized, and studied as models for proposed intermediates in various homogeneous catalytic reactions. Here we discuss two examples. Complex 2.4 is proposed as a model that shows the mode of interaction between an organic hydroperoxide and high-valent metal ions such as Ti4+, V5+, and Mo6+. This type of interaction is considered to be necessary for the oxygen atom transfer from the hydroperoxide to an alkene to give an epoxide (see Chapter 8). 

Subsequently, RR was used to successfully detect structural changes between the oxidized and reduced forms of both DMSOR and BSOR that are consistent with the proposed oxygen atom transfer mechanism of the catalytic reaction (95, 97). These experiments make use of the readily measurable isotopic shifts in vibration frequency between ieO=Mo and lsO=Mo to follow the fate of the oxygen atom removed from DMSO (or BSO) by the Mo. In this way, the clean transfer of 180 from DMSlsO to Mo(IV) to yield the oxidized form of the active site as Mo(VI)=180 was directly observed as well as the substrate-bound intermediate, (DMS180)Mo(IV). Further discussion of the technique of RR applied to metal dithiolenes and dithiolene-containing enzymes is included in Chapter 4 in this volume (98). 

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