ChemInform Abstract: X‐Ray Crystal Structure of cyclo‐Tetrakis(m‐phenylenesulfide).

Benzoyl-Substituted Tetrathia[1.1.1.1]metacyclophanes: High-Yield Synthesis, Crystal Structure, and Redox Properties

“…Surprisingly, the fine structure of the experimental spectra obtained in frozen THF matrix can be simulated by a quartet (S ϭ 3/ 2) absorption with the zero-field parameters D ϭ 5.75 mT and E ϭ 0.3 mT (Figure 4b). For the parent compound of the neutral macrocycles, a 1,3-alternate conformation is found, which is in good agreement with the solid state structure of 7e as well as that of tetrathia[1.1.1.1]metacyclophane [15] itself, thereby proving the reliability of the method. In contrast, the macrocycle 7d yielded only one single species upon reduction, which was a monoanion radical characterized by hyperfine coupling constants a H ϭ 1.58, 1.18, 1.10 and 0.5 mT, derived from high resolution electron-nuclear double-resonance (ENDOR) experiments.…”

“…The unsubstituted meta-phenylene subunits are lying on one side of this plane, whereas the substituted ones are on the other side. The conformation of the macrocyclic core is similar to that of the unsubstituted parent compound tetrathia[1.1.1.1]metacyclophane [15] . Thus, the alkyl-substituted benzoyl side groups are pointing away from the macrocyclic core, giving rise to an oval molecular shape.…”

“…3,5,17,8,15,tetrathia[1.1.1.1]metacyclophane (7a): The solid product was chromatographed on silica gel with petroleum ether/dichloromethane (1:4). The major fraction Eur.…”