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Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions, [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen−Chalcogen Bonded Dimers and a Novel Selone

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Konu, J., Chivers, T., & Tuononen, H. (2010). Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions, [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen−Chalcogen Bonded Dimers and a Novel Selone. Chemistry - A European Journal, 16(43), 12977-12987. https://doi.org/10.1002/chem.201001699
Published in
Chemistry - A European Journal
Authors
Konu, Jari |
Chivers, Tristram |
Tuononen, Heikki
Date
2010
Discipline
Epäorgaaninen ja analyyttinen kemiaInorganic and Analytical Chemistry
Copyright
© 2010 Wiley-VCH Verlag GmbH & Co. This is a final draft version of an article whose final and definitive form has been published by Wiley. Published in this repository with the kind permission of the publisher.

 
The lithium salts of the chalcogenocarbonyl dianions [(E)C(PPh2S)2]2− (E=S (4 b), Se (4 c)) were produced through the reactions between Li2[C(PPh2S)2] and elemental chalcogens in the presence of tetramethylethylenediamine (TMEDA). The solid-state structure of {[Li(TMEDA)]2[(Se)C(PPh2S)2]}—[{Li(TMEDA)}24 c]—was shown to be bicyclic with the Li+ cations bis-S,Se-chelated by the dianionic ligand. One-electron oxidation of the dianions 4 b and 4 c with iodine afforded the diamagnetic complexes {[Li(TMEDA)]2[(SPh2P)2CEEC(PPh2S)2]} ([Li(TMEDA)]27 b (E=S), [Li(TMEDA)]27 c (E=Se)), which are formally dimers of the radical anions [(E)C(PPh2S)2]−. (E=S (5 b), Se (5 c)) with elongated central E[BOND]E bonds. Two-electron oxidation of the selenium-containing dianion 4 c with I2 yielded the LiI adduct of a neutral selone {[Li(TMEDA)][I(Se)C(PPh2S)2]}—[{LiI(TMEDA)}6 c]—whereas the analogous reaction with 4 b resulted in the formation of 7 b followed by protonation to give {[Li(TMEDA)][(SPh2P)2CSS(H)C(PPh2S)2]}—[Li(TMEDA)]8 b. Attempts to identify the transient radicals 5 b and 5 c by EPR spectroscopy in conjunction with DFT calculations of the electronic structures of these paramagnetic species and their dimers are also described. The crystal structures of [{Li(TMEDA)}24 c], [{LiI(TMEDA)}6 c]⋅C7H8, [Li(TMEDA)]27 b⋅(CH2Cl2)0.33, [Li(THF)2]27 b, [Li(TMEDA)]27 c, [Li(TMEDA)]8 b⋅(CH2Cl2)2 and [Li([12]crown-4)2]8 b were determined and salient structural features are discussed. ...
Publisher
Wiley
ISSN Search the Publication Forum
0947-6539
Keywords
kalkogeenikarbonyylidianionit chalcogenocarbonyl dianions
DOI
https://doi.org/10.1002/chem.201001699
URI

http://urn.fi/URN:NBN:fi:jyu-201511243775

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/20145369

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  • Matemaattis-luonnontieteellinen tiedekunta [4568]

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