Peloquin Andrew J, Alapati Srikar, McMillen Colin D, Hanks Timothy W, Pennington William T
Department of Chemistry, Clemson University, Clemson, SC 29634, USA.
Department of Chemistry, Furman University, Greenville, SC 29613, USA.
Molecules. 2021 Aug 17;26(16):4985. doi: 10.3390/molecules26164985.
Through variations in reaction solvent and stoichiometry, a series of S-diiodine adducts of 1,3- and 1,4-dithiane were isolated by direct reaction of the dithianes with molecular diiodine in solution. In the case of 1,3-dithiane, variations in reaction solvent yielded both the equatorial and the axial isomers of S-diiodo-1,3-dithiane, and their solution thermodynamics were further studied via DFT. Additionally, S,S'-bis(diiodo)-1,3-dithiane was also isolated. The 1:1 cocrystal, (1,4-dithiane)·(I) was further isolated, as well as a new polymorph of S,S'-bis(diiodo)-1,4-dithiane. Each structure showed significant S···I halogen and chalcogen bonding interactions. Further, the product of the diiodine-promoted oxidative addition of acetone to 1,4-dithiane, as well as two new cocrystals of 1,4-dithiane-1,4-dioxide involving hydronium, bromide, and tribromide ions, was isolated.
通过改变反应溶剂和化学计量比，使1,3-二硫烷和1,4-二硫烷与分子碘在溶液中直接反应，分离得到了一系列1,3-和1,4-二硫烷的S-二碘加合物。对于1,3-二硫烷，改变反应溶剂可得到S-二碘-1,3-二硫烷的赤道式和轴向异构体，并通过密度泛函理论（DFT）进一步研究了它们的溶液热力学。此外，还分离得到了S,S'-双（二碘）-1,3-二硫烷。进一步分离得到了1:1共晶体（1,4-二硫烷）·（I）以及S,S'-双（二碘）-1,4-二硫烷的一种新多晶型物。每个结构都显示出显著的S···I卤键和硫属元素键相互作用。此外，还分离得到了碘促进丙酮与1,4-二硫烷发生氧化加成反应的产物，以及1,4-二硫烷-1,4-二氧化物与水合氢离子、溴离子和三溴离子形成的两种新共晶体。
