110613-28-0Relevant academic research and scientific papers
Mechanistic aspects of the oxidation of phosphines and related substrates by trans-Ru(VI)(TMP)(O)2; TMP = dianion of 5,10,15,20-tetramesitylporphyrin
Cheng, Stephen Y.S.,James, Brian R.
, p. 91 - 102 (1997)
The stoichiometric oxidations of some P(p-X-C6H4)3 compounds (X = OMe, Me, H, F, Cl and CF3), AsPh3 and SbPh3 by trans-Ru(VI)(TMPO)2 (1) in benzene solution generate the corresponding oxides and Ru(II)(TMP)(L) species (L = P(p-X-C6H4)3, AsPh3, SbPh3). Stopped-flow kinetic data are consistent with a mechanism involving formation (within a k1 step) of Ru(IV)(TMP)(O)(OL) which then reversibly dissociates the OL ligand to generate Ru(IV)(TMP)(O); this disproportionates to Ru(VI)(TMP)(O)2 and Ru(II)(TMP), which forms Ru(II)(TMP)(L). δH1(+) values for the phosphine systems vary from 18 to 21 kJ mol-1, increasing with decreasing electron density at the phosphorus, while ΔS1(+) values become more favorable (-94 to -78 J mol-1 K-1) with increasing molecular mass of the substituent. Preliminary kinetic data on the O2-oxidations of the substrates catalyzed by (1) under 1 atm of air are presented.
