Reactivity of Fluoro‐Substituted Bis(thiocarbonyl) Donors with Diiodine: An XRD, FT–Raman, and DFT Investigation

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.

Bonding Analysis in Homo‐ and Hetero‐Trihalide Species: A Charge Displacement Study

“…The I 3 – macro‐anion has been optimized in the gas phase by using the mPW1PW functional, which already proved to perform well for halide systems, the MCDHF‐adjusted small‐core pseudo‐potential and the def2‐QZVP basis set (see Computational Details). In the equilibrium structure, I(s) , the geometry is symmetrical with d I–I = 2.930 Å (Scheme ).…”

Gold Thione Complexes

“…The HOMO-1 and HOMO calculated at DFT level for Et 4 todit are built up of the in-phase and out-of-phase combinations of the non-bonding lone pairs localized on the sulfur atoms, perpendicular to the imidazole plane, respectively, with remarkably negative NBO charges [9]. The terminal thiocarbonyl groups are potential donors not only towards molecular acids, [8][9][10] but also towards transition metal ions [11,12]. We have, therefore, studied the coordination properties of this ligand towards gold(I) and gold(III) derivatives.…”

“…Tetrathiocino-diimidazolyl species also contains two C=S groups that can behave as donors towards Lewis acids [8][9][10]. In particular, the ligand Et 4 todit (4,5,6,7-tetrathiocino-[1,2-b:3,4-b']-diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione) (Scheme 1) features very distant positions of the thiocarbonyl groups that make this molecule capable to act as bidentate bridging ligand.…”

Iodo(trisyl)sulfane: Reactivity of a Stable Alkanesulfenyl Iodide towards Antithyroid Drugs

“…Force constants and the resulting vibrational IR‐ and Raman‐active frequencies were computed by analytically determining the second derivatives of the energy with respect to the Cartesian nuclear coordinates at the optimized geometries. The program Pyfreq31 was used to analyze vibrational spectra, and Molden 5.032 was used to investigate the molecular‐orbital (MO) shapes.…”