Formation of T‐Shaped versus Charge‐Transfer Molecular Adducts in the Reactions Between Bis(thiocarbonyl) Donors and Br2 and I2 |
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| Authors: | Dr Annalisa Mancini Dr M Carla Aragoni Dr Neil Bricklebank Dr Carlo Castellano Prof Francesco Demartin Prof Francesco Isaia Prof Vito Lippolis Dr Anna Pintus Dr Massimiliano Arca |
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| Institution: | 1. Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, Cagliari (Italy), Fax: (+39)?070‐675‐4456;2. Biomedical Research Centre, Sheffield Hallam University, Sheffield S1 1WB (UK);3. Dipartimento di Chimica, Università degli Studi di Milano via Golgi 19, 20133 Milano (Italy) |
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| Abstract: | The reactions of 4,5,6,7‐tetrathiocino‐1,2‐b:3,4‐b′]‐1,3,8,10‐tetrasubstituted‐diimidazolyl‐2,9‐dithiones (R2,R′2‐todit; 1 : R=R′=Et; 2 : R=R′=Ph; 3 : R=Et, R′=Ph) with Br2 exclusively afforded 1:1 and 1:2 “T‐shaped” adducts, as established by FT‐Raman spectroscopy and single‐crystal X‐ray diffraction in the case of complex 1? 2 Br2. On the other hand, the reactions of compounds 1 – 3 with molecular I2 provided charge‐transfer (CT) “spoke” adducts, among which the solvated species 3? 2 I2 ? (1?x)I2 ? x CH2Cl2 (x=0.94) and ( 3 )2 ? 7 I2 ? x CH2Cl2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT‐Raman spectroscopy and supported by theoretical calculations at the DFT level. |
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| Keywords: | adducts chalcogens charge transfer density functional calculations halogens |
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