title: Kinetic effects of increased proton transfer distance on proton-coupled oxidations of phenol-amines.
abstract: To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh(2)NH(2) substituent (1). Spectroscopic, structural, thermochemical, and computational studies show that the two amino-phenols are very similar, except that the O···N distance (d(ON)) is >0.1 Å longer in 2 than in 1. The difference in d(ON) is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations (•)OAr-NH(3)(+) by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. 2 orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C(6)H(4)OMe)(3)(•+) (3a(+)) occurs at (1.4 ± 0.1) × 10(4) M(-1) s(-1), only a factor of 2 slower than the closely related reaction of 1 with N(C(6)H(4)OMe)(2)(C(6)H(4)Br)(•+) (3b(+)). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG° (2 + 3a(+)) = +0.078 V versus ΔG° (1 + 3b(+)) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δ ln(k)/Δ ln(K(eq))). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly anharmonic O···H···N potential energy surface and the influence of proton vibrational excited states.
authors.affiliation: Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA. todd.markle@fotomol.uu.se
authors.forename: Todd F
authors.initials: TF
authors.lastname: Markle
authors.forename: Ian J
authors.initials: IJ
authors.lastname: Rhile
authors.forename: James M
authors.initials: JM
authors.lastname: Mayer
mesh_terms: D000588:Amines / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D011522:Protons; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000588:Amines; D010636:Phenols; D011522:Protons