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The Influence of Ligand Substitution at the Electron Donor Center in Molecular Cyano‐Bridged Mixed‐Valent Co III /Fe II and Co III /Ru II Complexes
Author(s) -
Bernhardt Paul V.,
Bozoglian Fernando,
FontBardía Mercè,
Martínez Manuel,
Meacham Andrew P.,
Sienra Beatriz,
Solans Xavier
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700731
Subject(s) - chemistry , ligand (biochemistry) , crystallography , metal , redox , coordination sphere , transition metal , electron transfer , stereochemistry , center (category theory) , group 2 organometallic chemistry , molecule , inorganic chemistry , crystal structure , catalysis , biochemistry , receptor , organic chemistry
In this paper we report a new variety of dinuclear cyano‐bridged Co III /M II (M = Fe or Ru) mixed‐valent complexes of the general formula [L n Co III (μ‐NC)M II (CN) x (bpy) y ] z + (where L n 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 M III/II redox potential significantly relative to the hexacyanometalate analogs we have reported previously. However, the metal‐to‐metal (M II to Co III ) 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 (M II to bpy) transitions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)