The Reaction of Hydroperoxides with Triphenylarsine and Triphenylstibine

Abstract

R. H I A~, CHRISTINE MCCOLEMAN, and G. R. HOWE. Can. J. Chem. 53,559 (1975). Triphenylstibine reduced r-Bu02H to r-BuOH almost as fast as Ph3P does, while triphenylarsine reacts only 1/60as fast. Both reductions are first-order ineach component; in ethanol k, for Ph3Sb and Ph3As are 106.7e-9.71RT and 109.1e-15.7RT; respectively. The reductions are not very sensitive to choice of solvent, but are strongly catalyzed by compounds of molybdenum and vanadium.The relative rate order PH3P 3 Ph3Sb > Ph3As is ascribed to two conflicting trends,availability of d-orbitals for T-bonding with peroxidic oxygen, and the Group VB to oxygen bond strength.R. HIATT, CHRISTINE MCCOLEMAN et G. R. HOWE. Can. J. Chem. 53,559 (1975). La triphenylstibine rkduit le r-Bu02H en r-BuOH presqu'aussi rapidement que le fait Ph3P; par ailleurs la triphenylarsine rtagif environ 60 fois moins rapidement. Chacune des reductions est du premier ordre en chacun des rkactifs; dans I'ethanol, les valeurs de k, pour Ph3Sb et Ph3As sont respectivement de 106.7e-9.71RT et l@.le-l5.7/RT. Les reductions ne sont pas sensibles a u choix du solvant mais sont fortement catalysees pardes composis du molybdkne et du vanadium.L'ordre relatif des vitesses Ph3P 3 Ph3Sb >Ph3As est attribue h deux tendances contradictoires soit la disponibilite d'orbitales pour former des liens T avec I'oxygkne du peroxyde et l a force de la liaison de I'oxygkne avec les eltments du groupe VB.[Traduit par le journal]

Reaction of organo-group 5A compounds with tert-butyl hydroperoxide

“…For the series of Ph3M compounds ( = P, As, Sb), we have observed that the reactivity with tert-butyl hydroperoxide decreases in the order triphenylphosphine (entry 8) > triphenylstibine (entry 18) > triphenylarsine (entry 17). During the course of our work, Hiatt et al 15 published similar rate constants for this series and also noted the anomaly of triphenylstibine reactivity. If one considers the reaction with tert-butyl hydroperoxide as a series of nucleophilic attacks on a soft electrophile, the antimony derivative is out of line, i.e., the reactivity order should be P > As > Sb.…”

“…However, triisopropyl (entry 13) and tri-2-ethylhexyl (entry 14) phosphites react with tertbutyl hydroperoxide more slowly than would be predicted by inductive effects alone, which suggests that steric factors do play a part in this reaction. During the course of our work, Hiatt et al 15 published similar rate constants for this series and also noted the anomaly of triphenylstibine reactivity. Using the Yukawa-Tsunol3 treatment to blend fractional amounts of g+ into the relationship does not improve the straight-line fit.…”

“…As shown in Table I, the reactivity of trivalent phosphorus compounds with tert-butyl hydroperoxide decreases as the substituents on phosphorus become increasingly electron withdrawing, i.e., in the order: trialkylphosphines (entries 1 and 2) > triarylphosphines (entries 6-10) > trialkyl phosphites (entries 11-14) > triphenyl phosphite (entry 15). This is as expected, since by far the predominant pathway of the reaction for both phosphites8 and triphenylphosphine3•5 is nucleophilically induced cleavage of the peroxide linkage.…”

Synthesis and Structural Characterization of Some Complexes of Hexa-coordinated Antimony

“…This fact confirms that the antimony atom in triphenylantimony o-phenylenedioxide is not accessible, and the coordinate Sb -O(P) bond formation is likely to take place at the earlier reaction step. Taking into account the corresponding rate constants for the reactions of triphenylphosphine and triphenylantimony with tert-butyl hydroperoxide, 21 we might suppose that the bond formation occures at the stage of antimony and phosphorus adducts (type 1) or when the oxygen of triphenylphosphine oxide coordinates to the antimony atom in triphenylantimony.…”

Tetraphenylantimony carboxylates in the cascade Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxide

“…The mechanism of the oxidation has been reported [9,10]. Ph 3 Sb forms either triphenylantimony diacetate Ph 3 Sb(OAc) 2 10 in the AcOH solution in the presence of hydroperoxide 3 (Eq.…”