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• W2400152421 endingPage "2840" @default.
• W2400152421 startingPage "2826" @default.
• W2400152421 abstract "The synthesis and characterization of a series of alkynyl half-sandwich complexes of type 2,5-((η5-C5H5)(dppe)MC≡C)2-cC4H2E (E = O (11), S (12); M = Fe (a), Ru (b); dppe = 1,2-bis(diphenylphosphino)ethane) are reported. The molecular structures of 11a and 12a,b in the solid state have been determined by single-crystal X-ray diffraction. The influence of different metals and the variation of the heterocyclic bridge on the electronic interactions between the terminal redox-active units in 11a,b and 12a,b was studied using electrochemical (cyclic and square wave voltammetry) and spectroelectrochemical (in situ UV–vis/NIR, ESR, and IR spectroscopy) methods and DFT calculations. Electrochemical studies demonstrated that mixed-valent species 11a,b+ and 12a,b+ exhibit high thermodynamic stabilities with respect to disproportionation (KC values from 6.87 × 104 to 9.33 × 105). In situ spectroelectrochemical ESR and IR measurements display delocalization of the single electron between the metal centers M/M+, revealing that within this setup five-membered heterocycles are well suited to promote intramolecular metal–metal interactions. Furthermore, the UV–vis/NIR spectra of mixed-valent 11a,b+ and 12a,b+ show intense, narrow, and nonsolvatochromic π(dπ) → π*(dπ) absorptions in the NIR region with a high-energy shoulder. Both experimental and computational results suggest that at least two thermally accessible rotation conformers of the organometallic termini of 11a,b and 12a,b contribute to the electronic spectra of these compounds. One of the conformers can clearly be characterized as a delocalized class III system, while the other shows a more localized behavior." @default.
• W2400152421 created "2016-06-24" @default.
• W2400152421 creator A5009182662 @default.
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• W2400152421 creator A5045885141 @default.
• W2400152421 creator A5085745309 @default.
• W2400152421 creator A5088536141 @default.
• W2400152421 date "2015-05-21" @default.
• W2400152421 modified "2023-10-10" @default.
• W2400152421 title "Five-Membered Heterocycles as Linking Units in Strongly Coupled Homobimetallic Group 8 Metal Half-Sandwich Complexes" @default.
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