Peroxo- compounds

AH of the commercial inorganic peroxo compounds except hydrogen peroxide are described herein, as are those commercial organic oxidation reactions that are beheved to proceed via inorganic peroxo intermediates. Ozonides and superoxides are also included, but not the dioxygen complexes of the transition metals. 

Actinide Peroxides. Many peroxo compounds of thorium, protactinium, uranium, neptunium, plutonium, and americium are known (82,89). The crystal stmctures of a number of these have been deterrnined. Perhaps the best known are uranium peroxide dihydrate [1344-60-1/, UO 2H20, and, the uranium peroxide tetrahydrate [15737-4-5] UO 4H2O, which are formed when hydrogen peroxide is added to an acid solution of a uranyl salt. 

Interest in the production of high-energy oxidizers for use in rocket motors has stimulated the study of peroxo compounds bound to highly electronegative groups during the past few decades. Although such applications have not yet materialized, numerous new compounds of this type... 

Other peroxo compounds SF500C(0)F, SF5OSF4OOSF5, SF5OSF4OOSF4OSF5,... 

As discussed in the exhaustive review of Notari [17], reaction temperature is of the upmost importance since Ti peroxo compounds decompose above 323 K. Solvents also have a remarkable effect in reaction rates and selectivity. 

Oxides of Platinum Metals Anodes of platinum (and more rarely of other platinum metals) are used in the laboratory for studies of oxygen and chlorine evolution and in industry for the synthesis of peroxo compounds (such as persulfuric acid, H2S2O8) and organic additive dimerization products (such as sebacic acid see Section 15.6). The selectivity of the catalyst is important for all these reactions. It governs the fraction of the current consumed for chlorine evolution relative to that consumed in oxygen evolution as a possible parallel reaction it also governs the current yields and chemical yields in synthetic electrochemical reactions. 

The rate constants for the 02 reaction do not vary significantly with different ligands (X = F, Cl, Br). The reaction of trans-[ r(CO)(CH3CN)(PPh3)2]1 with 102 is slightly slower than for the halide analogues.621 The peroxo compounds do not react with alkenes. 

Due to the limited extent of this paper, we mention only some positive results achieved in the orientation to two main directions i.e. to oxidative principles and to alcoholates in aprotic solvents. The research of oxidative principles (see e.g. [9]), involved the use of compounds with active chlorine, active iodine, peroxo-compounds, various mixtures of these compounds, as well as the use of oxidative agents with enhancing solubility and thus decontamination efficiency by adding detergents. It can... 

Peroxide titanate complexes, 25 98 Peroxide value, 20 827 in soap making, 22 736 Peroxidic compounds, 25 42 Peroxoborates, names, CAS numbers, and IUPAC names of, 18 398t Peroxocarbonates, 28 401 Peroxo compounds, 28 392-393, 397 Peroxodisulfate ion, 28 408 Peroxodisulfates, 28 392, 408-410 Peroxodisulfate salts, 28 418 uses for, 28 408-409 Peroxodisulfuric acid, 28 407 408 Peroxohydrate(s), 24 40 28 411—415 of melamine, 28 415 stabilization of, 28 413 Peroxo molybdate complexes, 2 7 22 Peroxomonophosphate ion, 28 403 Peroxomonophosphoric acid, 28 403 Peroxomonosulfates, 28 406 407... 

Mechanism of Olefin Epoxidation by Transition Metal Peroxo Compounds... 

During the last three decades, peroxo compounds of early transition metals (TMs) in their highest oxidation state, like TiIV, Vv, MoVI, WV1, and Revn, attracted much interest due to their activity in oxygen transfer processes which are important for many chemical and biological applications. Olefin epoxidation is of particular significance since epoxides are key starting compounds for a large variety of chemicals and polymers [1]. Yet, details of the mechanism of olefin epoxidation by TM peroxides are still under discussion. 

Figure I. Insertion and direct transfer mechanisms of ethene epoxidation by TM peroxo compounds, exemplified for a Mo complex.

An important finding is that all peroxo compounds with d° configuration of the TM center exhibit essentially the same epoxidation mechanism [51, 61, 67-72] which is also valid for organic peroxo compounds such as dioxiranes and peracids [73-79], The calculations revealed that direct nucleophilic attack of the olefin at an electrophilic peroxo oxygen center (via a TS of spiro structure) is preferred because of significantly lower activation barriers compared to the multi-step insertion mechanism [51, 61-67]. A recent computational study of epoxidation by Mo peroxo complexes showed that the metallacycle intermediate of the insertion mechanism leads to an aldehyde instead of an epoxide product [62],... 

Despite of the common reaction mechanism, peroxo complexes exhibit very different reactivities - as shown by the calculated activation energies -depending on the particular structure (nature of the metal center, peroxo or hydroperoxo functionalities, type and number of ligands). We proposed a model [72, 80] that is able to qualitatively rationalize differences in the epoxidation activities of a series of structurally similar TM peroxo compounds CH3Re(02)20-L with various Lewis base ligands L. In this model the calculated activation barriers of direct oxygen transfer from a peroxo group... 

These findings for Re peroxo complexes are in striking contrast with Ti and V catalyzed reactions [41, 51, 52, 111, 113] in which the metal-alcoholate bond drives the allylic OH directivity. We recall that the formation of alcoholate intermediates was also rejected for epoxidations of allylic alcohols with Mo and W peroxo compounds while H-bonding (between OH and the reacting peroxo fragment) was considered consistent with kinetic data for these complexes [115]. 

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