Iron versus Ruthenium Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires
| Autor: | Mark W. Whiteley, Simon Gückel, Alexandre N. Sobolev, Claude Lapinte, Josef B. G. Gluyas, Martin Kaupp, Jean-François Halet, Sarah El-Tarhuni, Paul J. Low |
|---|---|
| Přispěvatelé: | Technical University of Berlin / Technische Universität Berlin (TU), The University of Western Australia (UWA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ARC [DP 140100855], DFG [KA1187/13-2], ARC Future Fellowship [FT 120100073], Alexander von Humboldt Foundation, Government of Libya, DAAD/Go8, Technische Universität Berlin (TU), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA) |
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
Valence (chemistry)
010405 organic chemistry Organic Chemistry chemistry.chemical_element Crystal structure 010402 general chemistry 01 natural sciences 0104 chemical sciences Hybrid functional Ruthenium Inorganic Chemistry Crystallography Molecular wire Delocalized electron Radical ion chemistry [CHIM]Chemical Sciences Physical and Theoretical Chemistry Conformational isomerism |
| Zdroj: | Organometallics Organometallics, 2018, 37 (9), pp.1432-1445. ⟨10.1021/acs.organomet.8b00099⟩ Organometallics, American Chemical Society, 2018, 37 (9), pp.1432-1445. ⟨10.1021/acs.organomet.8b00099⟩ |
| ISSN: | 0276-7333 1520-6041 |
| DOI: | 10.1021/acs.organomet.8b00099⟩ |
| Popis: | International audience; The electronic structures of the prototypical bimetallic buta-1,3-diyn-1,4-diyl-bridged radical cation complexes [{M(dppe)Cp'}(2)(mu-C CC C)](+) (M= Fe, Cp' = Cp* (1a), Cp (1b); M = Ru, Cp' = Cp* (2a), Cp (2b)) have been (re)investigated using a combination of UV-vis-NIR and IR spectroelectrochemistry, and quantum chemical calculations based on both dispersion-corrected global (BLYP35-D3) and local (Lh-SsirPW92-D3) hybrid functionals. Following analysis of new and existing data, including the IR-active v(C C) bands, the iron compounds [1](+) are reclassified as valence-trapped (Robin and Day Class II) mixed-valence complexes, in contrast to the ruthenium complexes [2](+), which are delocalized (Robin and Day Class III) systems. All members of the series exist as a thermally populated distribution of conformers in solution, and the overlapping spectroscopic profiles make the accurate extraction of the parameters necessary for the analysis of [1](+) and [2](+) within the framework of the Marcus-Hush model extremely challenging. Analysis of the spin-density distributions from a range of conformational minima provides an alternative representation of the degree of charge localization, and a comparison between members of the series is presented. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|