Skip navigation
University library of Heidelberg
Availability: reference only

Verfügbarkeit
Location: ---
Copies: ---
heiBIB
 Online resource
Verfasst von:Comba, Peter [VerfasserIn]   i
 Kerscher, Marion [VerfasserIn]   i
 Roodt, Andreas [VerfasserIn]   i
Titel:Slow electron self-exchange in spite of a small inner-sphere reorganisation energy
Titelzusatz:the electron-transfer properties of a Copper complex with a Tetradentate Bispidine ligand
Verf.angabe:Peter Comba, Marion Kerscher, and Andreas Roodt
E-Jahr:2004
Jahr:20 October 2004
Umfang:6 S.
Fussnoten:Gesehen am 22.02.2018
Titel Quelle:Enthalten in: European journal of inorganic chemistry
Ort Quelle:Weinheim : Wiley-VCH, 1998
Jahr Quelle:2004
Band/Heft Quelle:(2004), 23, Seite 4640-4645
ISSN Quelle:1099-0682
Abstract:The electron self-exchange rate of [Cu(L)(OH2)]2+/1+, kexp11 (298.13 K) = 15 ± 11 m−1s−1 {L = dimethyl 3,7-dimethyl-9oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate}, was determined by a cross reaction. The analysis, based on classical Marcus theory, indicates that this relatively slow rate is to a large extent due to enthalpic terms (ΔG‡,exp11 = 62.8 ± 3.5 kJ·mol−1, ΔH‡,exp11 = 36.0 ± 2.7 kJ·mol−1 and ΔS‡,exp11 = −92 ± 10 J·mol−1K−1). The activation entropy is significant but not unusually large and the calculated outer-sphere reorganization energy, ΔG*,calcout = 20.5 kJ·mol−1, is at least of the same order of magnitude as the calculated inner-sphere reorganisation energy ΔG*,calcin = 18.6 kJ·mol−1, i.e. the deformation of the solvent sheath is a major reason for the slow electron transfer rate. This is believed to be due to the highly elastic coordination geometry which leads to little strain upon distortion enforced by the electron transfer but to comparably large structural changes and, hence, to a large outer-sphere reorganisation term.
DOI:doi:10.1002/ejic.200400518
URL:Bibliographic entry. University members only receive access to full-texts for open access or licensed publications.

Volltext: http://dx.doi.org/10.1002/ejic.200400518
 Volltext: http://onlinelibrary.wiley.com/doi/10.1002/ejic.200400518/abstract
 DOI: https://doi.org/10.1002/ejic.200400518
Datenträger:Online-Ressource
Sprache:eng
Sach-SW:Cross reaction
 Kinetics
 Marcus theory
 Molecular mechanics
 Outer-sphere electron transfer
K10plus-PPN:1570104948
Verknüpfungen:→ Journal

Permanent link to this item:  https://katalog.ub.uni-heidelberg.de/titel/68223187   QR-Code
zum Seitenanfang