%0 Journal Article %T Iron versus Ruthenium Clarifying the Electronic Differences between Prototypical Mixed-Valence Organometallic Butadiyndiyl Bridged Molecular Wires %+ Technical University of Berlin / Technische Universität Berlin (TU) %+ The University of Western Australia (UWA) %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Gueckel, Simon %A Gluyas, Josef B. G. %A El-Tarhuni, Sarah %A Sobolev, Alexandre N. %A Whiteley, Mark W. %A Halet, Jean-François %A Lapinte, Claude %A Kaupp, Martin %A Low, Paul J. %Z ARC [DP 140100855] %Z DFG [KA1187/13-2] %Z ARC Future Fellowship [FT 120100073] %Z Alexander von Humboldt Foundation %Z Government of Libya %Z DAAD/Go8 %< avec comité de lecture %@ 0276-7333 %J Organometallics %I American Chemical Society %V 37 %N 9 %P 1432-1445 %8 2018-05-14 %D 2018 %R 10.1021/acs.organomet.8b00099 %Z Chemical SciencesJournal articles %X 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. %G English %2 https://univ-rennes.hal.science/hal-01807083/document %2 https://univ-rennes.hal.science/hal-01807083/file/Gueckel_Iron%20versus%20Ruthenium.pdf %L hal-01807083 %U https://univ-rennes.hal.science/hal-01807083 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_OMC2012 %~ ISCR-OMC %~ ISCR-CTI %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ UR1-MMS %~ TEST2-HALCNRS