The influence of ligand substitution at the electron donor center in molecular cyano-bridged mixed-valent CoIII/FeII and CoIII/RuII complexes

Bernhardt, Paul V., Bozoglian, Fernando, Font-Bardía, Mercè, Martínez, Manuel, Meacham, Andrew P., Sienra, Beatriz and Solans, Xavier (2007) The influence of ligand substitution at the electron donor center in molecular cyano-bridged mixed-valent CoIII/FeII and CoIII/RuII complexes. European Journal of Inorganic Chemistry, 2007 33: 5270-5276. doi:10.1002/ejic.200700731


Author Bernhardt, Paul V.
Bozoglian, Fernando
Font-Bardía, Mercè
Martínez, Manuel
Meacham, Andrew P.
Sienra, Beatriz
Solans, Xavier
Title The influence of ligand substitution at the electron donor center in molecular cyano-bridged mixed-valent CoIII/FeII and CoIII/RuII complexes
Formatted title
The influence of ligand substitution at the electron donor center in molecular cyano-bridged mixed-valent CoIII/FeII and CoIII/RuII complexes
Journal name European Journal of Inorganic Chemistry   Check publisher's open access policy
ISSN 1099-0682
1434-1948
Publication date 2007-11
Sub-type Article (original research)
DOI 10.1002/ejic.200700731
Volume 2007
Issue 33
Start page 5270
End page 5276
Total pages 7
Place of publication Weinheim, Germany
Publisher Wiley - VCH Verlag
Collection year 2008
Language eng
Subject C1
780103 Chemical sciences
250201 Transition Metal Chemistry
Formatted abstract
In this paper we report a new variety of dinuclear cyano-bridged CoIII/MII (M = Fe or Ru) mixed-valent complexes of the general formula [L𝑛CoIII(μ-NC)MII(CN)𝑥(bpy)𝑦]𝑧+ (where L𝑛 represents a pentaamine macrocycle and M = Fe or Ru with 𝑥 = 4, 𝑦 = 1 and 𝑧 = 1 or 𝑥 = 2, 𝑦 = 2 and 𝑧 = 3)]. The incorporation of the bpy ligand in place of cyano ligands within the coordination sphere raises the MIII/II redox potential significantly relative to the hexacyanometalate analogs we have reported previously. However, the metal-to-metal (MII to CoIII) charge-transfer transitions are shifted to lower energies in accordance with Hush theory as a result of a decreased reorganizational energy component, which result in them overlapping with more intense MLCT (MII to bpy) transitions.
Keyword Chemistry, Inorganic & Nuclear
Mixed-valent compounds
Cyanides
Binuclear complexes
Cobalt(III)
Temperature
Ruthenium
Pressure
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 16 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 14 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Mon, 18 Feb 2008, 15:49:23 EST