Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes. - Université de Rennes Access content directly
Journal Articles Inorganic Chemistry Year : 2015

Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

Abstract

Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known sep. to act as good electron donor mols. For a study of the interaction between both electrophores, two types of complexes were synthesized and characterized. The 1st type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the 2nd type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochem. properties of these complexes with those of models of each sep. electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a 1st oxidn. potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calcns. suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The x-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier MOs. UV-visible-NIR spectroelectrochem. studies confirm this electronic delocalization within the TTF dithiolate ligand. [on SciFinder(R)]
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Dates and versions

hal-01151354 , version 1 (12-05-2015)

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Nathalie Bellec, Antoine Vacher, Frédéric Barrière, Zijun Xu, Thierry Roisnel, et al.. Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.. Inorganic Chemistry, 2015, 54 (10), pp.5013-5020. ⟨10.1021/acs.inorgchem.5b00632⟩. ⟨hal-01151354⟩
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