Journal of the American Chemical Society p. 4106 - 4115 (1982)
Update date:2022-08-11
Topics:
Thompson, Mark S.
Meyer, Thomas J.
Kinetic and mechanistic studies have been carried out on the oxidation of 2-propanol to acetone in water by RuIV(trpy)(bpy)O2+ (trpy is 2,2',2''-terpyridine; bpy is 2,2'-bipyridine) and in acetonitrile by RuIV(bpy)2(py)O2+ (py is pyridine).The reactions proceed by oxidation of 2-propanol by Ru(IV) followed by a slower oxidation by the Ru(III) complexes Ru(trpy)(bpy)OH2+ or Ru(bpy)2(py)OH2+.For the reactions: in water, kIV(25 deg C) = 6.7 * 10-2 M-1 s-1, ΔH<*> = 9 +/- kcal/mol, ΔS<*> = -34 +/- 4 eu, kH/kD = 18 +/- 3; in <(CH3)2CHOH/(CD3)2CDOH>, kIII(25 deg C) = 6 * 10-5 M-1 s-1, ΔH<*> = 19 +/- 2 kcal/mol, ΔS<*> = -12 +/- 6 eu, kH/kD = 2.7 +/- 1.4.An 18O-labeling experiment in 2-propanol and a spectral experiment in CH3CN show that oxo transfer from the oxidant to the substrate does not occur.It is concluded that the most likely mechanism of oxidation for Ru(IV) is a concerted, two-electron hydride transfer from the α-C-H bond to RuIV=O with the oxo group acting as a lead-in atom to the Ru(IV) acceptor site.The Ru(III) reaction in water appears to occur by an initial one-electron, outer-sphere electron transfer.In acetonitrile there appears to be a change in mechanism for this reaction, apparently to a H-atom transfer, once again involving the α-C-H group.For this path: k(25 deg C) = (8+/- 2) * 10 -4 M-1 s-1, ΔH<*> = 10 +/- 2 kcal/mol, ΔS<*> = -38 +/- 7 eu, kH/kD <*> 8.
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