Kinetics and mechanism of oxidation of triphenylphosphine by hydrogen peroxide

Concerted Multiproton–Multielectron Transfer for the Reduction of O2 to H2O with a Polyoxovanadate Cluster

“…In an attempt to verify this proposed mechanistic pathway, O 2 was added to a solution of the fully reduced cluster in MeCN- d 3 in the presence of excess triphenylphosphine. Previous work has reported PPh 3 as an excellent trap for H 2 O 2 ; , H 2 O 2 rapidly combines with the triarylphosphine to produce the oxidized product, triphenylphosphine oxide. Indeed, analysis of the result of this experiment obtained by 1 H and 31 P NMR spectroscopies reveals the phosphine oxide product is formed upon exposure of V 6 O 7 (OH) 6 to O 2 (Figures S11 and S12).…”

Post-assembly Modification of Phosphine Cages Controls Host–Guest Behavior

“…We then probed the direct addition of hydrogen peroxide as a means to transform cage 2 to cage 3. 35 The addition of H2O2 (16 equiv) to 2 led, within 10 minutes, to the formation of several intermediate species (Figure 2b). After 16 hours at 25 °C these species disappeared, forming cage 3, whose NMR spectra matched those of a sample prepared directly from the phosphine oxide ligand, indicating that in situ oxidation occurred cleanly ( Figure 2).…”

Sterically constrained tricyclic phosphine: redox behaviour, reductive and oxidative cleavage of P–C bonds, generation of a dilithium phosphaindole as a promising synthon in phosphine chemistry

“… 1,7 The oxidant H 2 O 2 reacts with tertiary phosphines by oxidation of the P atoms, formation of phosphine oxides and release of water. 35,36 Recently the highly selective synthesis of Ph 3 PO in a 100% yield was achieved on such a route. 36 The highly strained ring system of compounds 3 may result in another reaction course, and we, therefore, treated a cooled (−78 °C) solution of 3a in n -pentane with a concentrated H 2 O 2 solution in water ( Scheme 6 ).…”