Synthesis and crystal structure of an arenesulfenyl iodide with unprecedented stability

Abstract

An arenesulfenyl iodide with unprecedented stability was synthesized by oxidation of a thiol bearing a novel bowl-type substituent with iodine, whose monomeric structure was determined by X-ray crystallographic analysis.

Halogen-bond geometry: a crystallographic database investigation of dihalogen complexes

“…For example, for IÐ IÁ Á ÁN, IÐIÁ Á ÁS and IÐIÁ Á ÁSe complexes we ®nd d 0 values of 1.733, 2.370 and 2.495 A Ê for the IÐN, IÐS and IÐSe bonds, respectively. The two latter values agree within 0.04 A Ê with the experimental values d(IÐS) = 2.396 A Ê , from the CSD structures GIGBED (Minkwitz et al, 1988) and JITQOS (Goto et al, 1998), and with d(IÐSe) = 2.528 A Ê in the FOHNEV (Du Mont et al, 1987) structure. However, the ®rst value departs severely from the value of 2.091 (35) A Ê for d(IÐN) obtained by averaging 13 NÐI values [HINXEH, HINXIL, HINXOR (Grebe et al, 1999), HMTNTI (Pritzkow, 1974a), IFORAM (Pritzkow, 1974b), REWXAS (Grebe et al, 1996), ZZZVCQ01 (Padmanabhan et al, 1990 and PYDTIN (Hartl & Ullrich, 1974)].…”

Green Preparation of Dibenzothiophene Derivatives Using 2‐Biphenylyl Disulfides in the Presence of Molecular Iodine and Its Application to Dibenzoselenophene Synthesis

“…On the basis of the above results, a plausible mechanism for the cyclization is shown in Scheme . Initially, the S–S bond of 2‐biphenylyl disulfide is oxidatively cleaved by I 2 to form intermediate A with an S–I bond that is highly reactive owing to its high level of polarity . Then, tricyclic intermediate B is formed by intramolecular S E Ar to the S–I bond.…”

Kinetic Stabilization of Highly Reactive Species Bearing Heteroatoms

“…To embody this concept, we have designed four types of bowl‐shaped molecules having substituents Ar 1 ‐, Ar 2 ‐, Bmt‐, and Bpq‐ and succeeded in the synthesis of stable compounds bearing some highly reactive functionalities, which are very susceptible to self‐dimerization, such as sulfenic acids (Ar 1 SOH 52 , Ar 2 SOH , BmtSOH ), selenenic acid (Ar 2 SeOH 53 , BmtSeOH ), sulfenyl iodide (BmtSI 54 , BpqSI ), and nitrosothiol (BpqSNO 55 , BmtSNO ) (Chart ). As anticipated, all of these compounds are quite stable toward dimerization, yet capable of reacting with relatively small molecules that can enter their cavities.…”