Phosphorus peroxides unsymmetrical

Numerous sulfur and phosphorus peroxy compounds such as monopersulfuric acid (Caro s acid, la), monopersulfate (Oxone, Ib), ammonium monopersulfate Ic, tetra n-butyl-ammonium monopersulfate Id, peroxydisulfates 2a and 2b", tetra n-butylammonium peroxydisulfate 2c, symmetrical bissulfonyl peroxide 3 , acyl sulfonyl peroxide 4 , unsymmetrical sulfonyl peroxide 5 , sulfinyl peroxy intermediates 6a, sulfonyl peroxy intermediate 6b, sulfonimidoyl peroxy intermediate 7, bis(diphenyl phosphinyl) peroxide 8 , unsymmetrical phosphorus peroxide 9 and phosphoranyl peroxy intermediate 10" are known. Recently, many researchers have shown interest in the preparation and... 

Since the first synthesis of the peroxyphosphoms ester 66 °, considerable efforts have been made to characterize the expanding chemistry of organophosphorus peroxy esters. Later, unsymmetrical phosphorus peroxides, such as peroxyphosphates 67 , peroxyphos-phonates 68 and peroxyphosphinates 69 , were reported. They can be prepared by the reactions of the chlorides and a tertiary carboxylic acid in the presence of base. 

Phosphorus peroxides, 1039-46 symmetrical, 1041-2 unsymmetrical, 1042-4 Photocalorimetry, ozonides, 165 Photochemistry... 

The mechanism for the thermal rearrangement of bis(diphenylphosphinyl) peroxide to an unsymmetrical anhydride (125) has been elucidated. An intramolecular hard-hard interaction between oxygen and phosphorus atoms results in a zwitterion intermediate which collapses via migration of a phenyl group from P to O (soft) with a concomitant 0-0 bond fission. 

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