The extent of metalmetal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)2-,(RhL2)2- and (FeCp)(RhL2)- (L2= 1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixedvalent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic ironrhodium as-indacenediide complexes, strong metalmetal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti FeRh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.
Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCP)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions
Benetollo F;Crociani L
2007
Abstract
The extent of metalmetal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)2-,(RhL2)2- and (FeCp)(RhL2)- (L2= 1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixedvalent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic ironrhodium as-indacenediide complexes, strong metalmetal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti FeRh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.File | Dimensione | Formato | |
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Descrizione: Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCP)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions
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