UPHILL ELECTRON-TRANSFER IN PENTAAMMINERUTHENIUM(III)-MODIFIED FERROCYTOCHROME-C - RATES, THERMODYNAMICS, AND THE MEDIATING ROLE OF THE RUTHENIUM MOIETY

Authors
SUN J WISHART JF ISIED SS
Citation
J. Sun et al., UPHILL ELECTRON-TRANSFER IN PENTAAMMINERUTHENIUM(III)-MODIFIED FERROCYTOCHROME-C - RATES, THERMODYNAMICS, AND THE MEDIATING ROLE OF THE RUTHENIUM MOIETY, Inorganic chemistry, 34(15), 1995, pp. 3998-4000
Citations number
19
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Inorganic chemistry → ACNP
ISSN journal
00201669
Volume
34
Issue
15
Year of publication
1995
Pages
3998 - 4000
Database
ISI
SICI code
0020-1669(1995)34:15<3998:UEIPF>2.0.ZU;2-H
Abstract
The rate of thermodynamically-unfavorable (uphill) Fe-II-to-Ru-III ele ctron transfer in pentaammineruthenium-modified horse-heart cytochrome c was obtained by using sufficiently high Co(oxalate)(3)(3-) concentr ations to saturate the pre-equilibrium. The rate of uphill intramolecu lar electron transfer at 25 degrees C is 0.40 s(-1) (Delta H-double da gger = 12.5 +/- 0.2 kcal mol(-1), Delta S-double dagger = -18.3 +/- 0. 7 cal deg(-1) mol(-1)). The net reaction thermodynamics are as follows : Delta G(o) = -0.125 eV, Delta H degrees = -9.0 +/- 0.2 kcal mol(-1), and Delta S degrees = -20.7 +/- 0.8 cal deg(-1) mol(-1).