Reactivity of Fluoro‐Substituted Bis(thiocarbonyl) Donors with Diiodine: An XRD,FT–Raman,and DFT Investigation |
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| Authors: | Dr. Annalisa Mancini Dr. M. Carla Aragoni Dr. Ann L. Bingham Dr. Carlo Castellano Dr. Susanne L. Coles Prof. Francesco Demartin Prof. Michael B. Hursthouse Prof. Francesco Isaia Prof. Vito Lippolis Dr. Giuseppe Maninchedda Dr. Anna Pintus Dr. Massimiliano Arca |
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| Affiliation: | 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. School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ (UK);3. Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133, Milano (Italy);4. Faculty of Science, King Abdulaziz University, Jeddah, 21588 (Saudi Arabia) |
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| Abstract: | The reactions of 1,3,8,10‐tetrakis(4′‐fluorophenyl)‐4,5,6,7‐tetrathiocino[1,2‐b:3,4‐b′]diimidazolyl‐2,9‐dithione ( 4 ) and molecular diiodine afforded spoke adducts with stoichiometries 4·I2 and 4? 3I2, isolated in the compound 4? 3I2 ? xCH2Cl2 ? (1?x)I2 (x=0.70), and characterized by single‐crystal XRD and FT–Raman spectroscopy. The nature of the reaction products was investigated under the prism of theoretical calculations carried out at the DFT level. The structural data, FT–Raman spectroscopy, and quantum mechanical calculations agree in indicating that the introduction of fluorophenyl substituents results in a lowering of the Lewis basicity of this class of bis(thiocarbonyl) donors compared with alkyl‐substituted tetrathiocino donors and fluorine allows for extended interactions that are responsible for solid‐state crystal packing. |
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| Keywords: | charge transfer density functional calculations fluorine halogens solid‐state structures |
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