Tuning the electronic communication in heterobimetallic mixed-valence ions of (1-ferrocenyl) and (2-ferrocenyl)indenyl rhodium isomers (Articolo in rivista)

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  • Tuning the electronic communication in heterobimetallic mixed-valence ions of (1-ferrocenyl) and (2-ferrocenyl)indenyl rhodium isomers (Articolo in rivista) (literal)
Anno
  • 2007-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1002/chem.200600724 (literal)
Alternative label
  • Santi S. ; Orian L. ; Durante C. ; Bisello A.; Benetollo F. ; Crociani L. ; Ganis P. ; Ceccon A. (2007)
    Tuning the electronic communication in heterobimetallic mixed-valence ions of (1-ferrocenyl) and (2-ferrocenyl)indenyl rhodium isomers
    in Chemistry - A European Journal
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Santi S. ; Orian L. ; Durante C. ; Bisello A.; Benetollo F. ; Crociani L. ; Ganis P. ; Ceccon A. (literal)
Pagina inizio
  • 1955 (literal)
Pagina fine
  • 1968 (literal)
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  • http://onlinelibrary.wiley.com/doi/10.1002/chem.200600724/pdf (literal)
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  • 13 (literal)
Rivista
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  • Very Important Paper (literal)
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  • 7 (literal)
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  • Scopu (literal)
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1-4,7,8 : Dipartimento di Scienze Chimiche, Università degli Studi di Padova / 5,6 : CNR, Istituto di Chimica Inorganica e delle Superfici, Padova (literal)
Titolo
  • Tuning the electronic communication in heterobimetallic mixed-valence ions of (1-ferrocenyl) and (2-ferrocenyl)indenyl rhodium isomers (literal)
Abstract
  • A series of heterobimetallic complexes of general structure [RhL2-{h5-(2-ferrocenyl)indenyl}] (L2=cod, nbd,L =CO; cod=cyclooctadiene; nbd=norbornadiene) has been synthesised with the aim of tuning the metal–metal interaction in their mixedvalence ions generated both by chemical and electrochemical oxidation,and the results are compared with those obtained for [RhL2{h5-(1-ferrocenyl)indenyl}] isomers. Crystallographic studies and DFT calculations provide a detailed description of the structural and electronic features of these complexes evidencing a significant difference in the extent of planarity of the flexible bridging ligand between the 1- and 2- ferrocenyl isomers. Independent experimental probes,in particular the potential splitting in the cyclic voltammograms and the IT bands in the near-IR spectra,are rationalised in the framework of Marcus–Hush theory and at quantum chemistry level by DFT and TD-DFT methods. These methods allow us to establish a trend based on the magnitude of iron–rhodium electronic coupling Hab ranging from valence trapped to almost delocalised ions. The quasi planar bridge and the olefin ancillary ligands make [Rh(nbd)-{h5-(2-ferrocenyl)indenyl}]+ and [Rh- (cod){h5-(2-ferrocenyl)indenyl}]+ rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species. (literal)
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