Iron Versus Ruthenium: Evidence for the Distinct Differences in the Electronic Structures of Hexa-1,3,5-triyn-1,6-diyl-bridged Complexes [Cp*(dppe)M}{μ-(C≡C)<sub>3</sub>}{M(dppe)Cp*}]<sup>+</sup> (M = Fe, Ru)
Simon Gückel, Parvin Safari, Seyed Mohammad Bagher Hosseini Ghazvini, Michael R. Hall, Josef B. G. Gluyas, Martin Kaupp, Paul J. Low
Abstract
The spectroelectrochemically generated infrared (IR) and near-infrared spectra of the homo-bimetallic, hexa-1,3,5-triyn-1,6-diyl-bridged complex cations [{Cp*(dppe)M}(μ-C≡CC≡CC≡C){M(dppe)Cp*}]+ (M = Fe, [1]+; Ru, [2]+) have been analyzed using density functional theory calculations based on global (BLYP35) and local (LH20t) hybrid functionals. The differences in the number of IR active ν(C≡CC≡CC≡C) modes in these complexes are attributed to the distinct electronic localization of the Fe(II)–Fe(III) mixed-valence cation [1]+ on the IR timescale, as opposed to the delocalized electronic character of [2]+.
Topics & Concepts
ChemistryDelocalized electronHEXABimetallic stripRutheniumDensity functional theoryValence (chemistry)InfraredCrystallographyInfrared spectroscopyElectronic structureStereochemistryComputational chemistryMetalPhysicsCatalysisOrganic chemistryOpticsBiochemistryMagnetism in coordination complexesOrganometallic Complex Synthesis and CatalysisMetal complexes synthesis and properties