Mechanistic information from the first volume profile analysis for intramolecular electron-transfer reactions: Tetraammine-ruthenium(ligand) complexes of cytochrome c
- Brookhaven National Lab., Upton, NY (United States). Dept. of Chemistry
- Univ. of Erlangen-Nuernberg, Erlangen (Germany). Inst. for Inorganic Chemistry
- Rutgers, The State Univ. of New Jersey, New Brunswick, NJ (United States). Dept. of Chemistry
The kinetics and thermodynamics of a series of reversible intramolecular electron-transfer reactions in systems of the type trans-(NH{sub 3}){sub 4}(L)Ru(His33)-cyt c(hh) and trans-(NH{sub 3}){sub 4}(L)Ru(His39)-cyt c(Ck), where L represents NH{sub 3}, isonicotinamide, 4-ethylpyridine, 3,5-lutidine, and pyridine, were studied as a function of pressure in order to construct the first complete volume profiles for such processes. The volume profiles demonstrate a significant partial molar volume increase associated with the reduction of the ruthenium center. In contrast to earlier results on a series of intermolecular reactions involving cytochrome c and the corresponding pentaammine complexes, for which the volume profiles are completely symmetrical, the studied intramolecular reactions exhibit asymmetric volume profiles. The overall volume changes can be accounted for in terms of electrostriction effects centered around the amine ligands on the ruthenium center. Explanations in terms of electronic and nuclear factors are offered to account for the asymmetrical nature of the volume profile.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 316218
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 24 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Substituted tetraammineruthenium cytochrome c derivatives: Chemistry and electron-transfer reactions
Dependence of intramolecular electron-transfer rates on driving force, pH, and temperature in ammineruthenium-modified ferrocytochromes c
Driving-force effects on the rate of long-range electron transfer in ruthenium-modified cytochrome C
Journal Article
·
Wed Jun 07 00:00:00 EDT 1995
· Inorganic Chemistry
·
OSTI ID:160096
Dependence of intramolecular electron-transfer rates on driving force, pH, and temperature in ammineruthenium-modified ferrocytochromes c
Journal Article
·
Wed Jan 22 23:00:00 EST 1997
· Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
·
OSTI ID:501916
Driving-force effects on the rate of long-range electron transfer in ruthenium-modified cytochrome C
Journal Article
·
Wed Jun 07 00:00:00 EDT 1989
· Journal of the American Chemical Society; (USA)
·
OSTI ID:6971186