- Oxidative addition reactions of compounds of the type (η5-C5Me5)Os(CO)LR (L = CO, PMe2Ph; R = alkyl). The role of oxidized intermediates in electrophilic cleavage reactions of osmium-carbon σ-bonds
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Compounds of the type Cp*Os(CO)LR (Cp* = η5-C6Me5; L = CO, PMe2Ph; R = Me, Et, i-Pr, CH2Ph), most of them new, have been prepared and their reactions with the electrophiles CF3CO2H, Br2, and HgBr2 have been investigated. All of the electrophiles oxidatively add to give labile, formally osmium(IV) complexes of the type [Cp*Os(CO)(L)(R)(E)]+X-, one of which, [Cp*Os(CO)(PMe2Ph)(Me)(HgBr)]+, has been isolated as the PF6- salt. In all cases, the osmium(IV) complexes decompose in solution to give the normal products of electrophilic cleavage.
- Johnston, Laura J.,Baird, Michael C.
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p. 2469 - 2475
(2008/10/08)
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- OXIDATIVE TRITYLDEMERCURATION OF ORGANOMERCURY COMPOUNDS
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In the reactions of Ph3CX (X=Cl, Br) with dialkylmercury compounds containing β-hydrogen atoms in the presence of oxygen the main result is determined by competition between two processes, i.e., β elimination (intermolecular hydride transfer) and oxidation with the formation of the peroxide Ph3COOAlk.By variation in the conditions of the reaction between dialkylmercury and triphenylbromomethane a method was found for the production of alkyl triphenylmethyl peroxides containing various primary and secondary alkyl radicals.The stereochemistry was investigated, and the mechanism of the formation of alkyl triphenylmethyl peroxides is discussed.
- Uglova, E. V.,Makhaev, V. D.,Reutov, O. A.
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p. 1386 - 1389
(2007/10/02)
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