Notes. Oxo transfer reactions. Mechanistic studies on the oxidation of triphenylphosphine by trans-[ Ru VI L(O)2]2+(L = 1,4,8,11 -tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane)
- 1 January 1989
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 2065-2067
- https://doi.org/10.1039/dt9890002065
Abstract
The mechanism for the oxidation of PPh3 to OPPh3 by trans-[ RuVIL(O)2]2+(L = 1,4,8,11- tetramethyl- 1,4,8,11 -tetra-azacyclotetradecane) in CH3CN was studied from 280 to 299 K. The rate law for the reaction is d [RuVI]/dt =k2[PPh3][RuVI]. At 299 K, k2, is (1.28 ± 0.1)× 102 dm3 mol–1 s–1. The ΔH‡ and ΔS‡ values are (8.7 ± 0.8) kcal mol–1 and –20 ± 2 cal K–1 mol–1 respectively. A direct comparison between the reactivities of trans-[RuVI(O)2]2+ and [RuIV(bipy)2(py)(O)]2+(bipy = 2,2′- bipyridine; py = pyridine) towards the oxidation of PPh3 shows the ruthenium(IV) complex to react 1 000 times faster.Keywords
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