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Abstract
An homologous series of divinylchalcogenophene-bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(µ-CH=CH-C4H2E-CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X-ray crystallography and various spectroscopic techniques. The single-crystal X-ray diffraction results reveal a distinct short/long bond-length alternation along the polyene-like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five-membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one-electron oxidation processes, the half-wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re-organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene-like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10-atom Ru–[4-s-cis-all-trans-(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.
Original language | English |
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Pages (from-to) | 5015-5026 |
Number of pages | 12 |
Journal | European Journal of Inorganic Chemistry |
Volume | 2017 |
Issue number | 43 |
DOIs | |
Publication status | Published - 24 Nov 2017 |
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- 1 Finished