SwePub
Sök i LIBRIS databas

  Utökad sökning

WFRF:(Markle J)
 

Sökning: WFRF:(Markle J) > (2011) > Kinetic Effects of ...

Kinetic Effects of Increased Proton Transfer Distance on Proton-Coupled Oxidations of Phenol-Amines

Markle, Todd F. (författare)
Dept of Chemistry, University of Washington
Rhile, Ian J. (författare)
Mayer, James M. (författare)
 (creator_code:org_t)
2011-10-11
2011
Engelska.
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 133:43, s. 17341-17352
  • Tidskriftsartikel (refereegranskat)
Abstract Ämnesord
Stäng  
  • 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 center dot center dot center dot N distance (d(ON)) is >0.1 angstrom longer in 2 than in 1. The difference in d(ON) is 0.13 +/- 0.03 angstrom from X-ray crystallography and 0.165 angstrom from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations (center dot)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)(center dot+) (3a(+)) occurs at (1.4 +/- 0.1) x 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)Me)(2)(C(6)H(4)Br)(center dot+) (3b(+)). This difference in rate constants is well accounted for by the slightly different free energies of reaction: Delta G(degrees) (2 + 3a(+)) = +0.078 V versus Delta G(degrees) (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 (Bronsted alpha, Delta ln(k)/Delta 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 center dot center dot center dot H center dot center dot center dot N potential energy surface and the influence of proton vibrational excited states.

Ämnesord

NATURVETENSKAP  -- Kemi (hsv//swe)
NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Publikations- och innehållstyp

ref (ämneskategori)
art (ämneskategori)

Hitta via bibliotek

Till lärosätets databas

Hitta mer i SwePub

Av författaren/redakt...
Markle, Todd F.
Rhile, Ian J.
Mayer, James M.
Om ämnet
NATURVETENSKAP
NATURVETENSKAP
och Kemi
Artiklar i publikationen
Journal of the A ...
Av lärosätet
Uppsala universitet

Sök utanför SwePub

Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.

 
pil uppåt Stäng

Kopiera och spara länken för att återkomma till aktuell vy