Synthesis and Structure of Bis(para‐methoxyphenyl)selenoxide and its Monohydrate. Theoretical Considerations of the Hydration of Diorganoselenium Oxides

Abstract

The title compound was prepared by base hydrolysis of (p‐MeOC6H4)2SeCl2 in water and isolated as the crystalline monohydrate, (p‐MeOC6H4)2SeO·H2O, in which the water molecule is associated via hydrogen‐bonding. Water‐free (p‐MeOC6H4)2SeO was obtained crystalline after drying and recrystallisation from toluene. Both crystal phases were investigated by single crystal X‐ray diffraction. Preliminary DFT calculations at the B3LYP/LANL2DZdp level of theory suggest that the hydrogen bonded complexes R2SeO·H2O (R = H, Me, Ph) are by 2.79, 3.36 and 11.10 kcal mol−1 more stable than the corresponding elusive diorganoselenium dihydroxides R2Se(OH)2. The hydrogen bond energies of R2SeO·H2O (R = H, Me, Ph) are 5.98, 7.18 and 5.89 kcal mol−1.

Zero-, one-, two- and three-dimensional supramolecular architectures sustained by Se…O chalcogen bonding: A crystallographic survey

“…The chemical diagrams for these species, i.e. 160 – 180 [93] , [104] , [105] , [113] , [188] , [206] , [207] , [208] , [209] , [210] , [211] , [212] , [213] , [214] , [215] , [216] , [217] , are shown in Fig. 15 .…”

“…The three selenoxides, 160 [104] , 161 [104] and 162 [206] , Fig. 16 a, feature C 2 O-donor sets and associate in their crystals to form linear, supramolecular chains via Se … O(nitro) interactions in 160 , and Se … O(methoxy) interactions in 161 and 162 .…”

Removal of Selenite from Water Using a Synthetic Dithiolate: An Experimental and Quantum Chemical Investigation

“…(inset) Crystal structure of ( p -MeOC 6 H 4 ) 2 SeO···H 2 O showing the hydrogen bonding similar to the hydrogen bonding calculated for 4 . The inset structure was redrawn from reference using the Mercury software program.…”

Recent advances in spirochalcogenurane stereochemistry—A mini review

“…This parallels the well-known tendency of the oxides to exist as hydrates in water solution because of stabilization of the chalcogen-oxygen single bonds. [44][45][46] While sulfoxides do not form hydrates, the corresponding telluroxides are completely hydrated in water. The selenoxides are stabilized by hydrogen bonding to a water molecule, as demonstrated by both X-ray crystallography and DFT calculations.…”

“…The selenoxides are stabilized by hydrogen bonding to a water molecule, as demonstrated by both X-ray crystallography and DFT calculations. 45 It was early recognized that spirochalcogenuranes could readily undergo a Berry pseudorotation 47 (BP) process, since a variable temperature 19 F-NMR spectrum of compound 15a (Scheme 7) showed four resonance signals below 21008C but only two at higher temperatures. 48 This signal collapse was attributed to a fast exchange within the exo-and the endo-located trifluoromethyl groups, respectively.…”