An experimental and theoretical insight into I2/Br2 oxidation of bis(pyridin‐2‐yl)diselane and ditellane
Abstract
The reactivity between bis(pyridin-2-yl)diselane oPy2Se2 and ditellane oPy2Te2 ( L1 and L2 , respectively; oPy=pyridyn-2-yl) and I2/Br2 is discussed. Single-crystal structure analysis revealed that the reaction of L1 with I2 yielded [(H L1 +)(I−)⋅5/2I2]∞ ( 1 ) in which monoprotonated cations H L1 + template a self-assembled infinite pseudo-cubic polyiodide 3D-network, while the reaction with Br2 yielded the dibromide HoPySeIIBr2 ( 2 ). The oxidation of L2 with I2 and Br2 yielded the compounds HoPyTeIII2 ( 3 ) and HoPyTeIVBr4 ( 6 ), respectively, whose structures were elucidated by X-ray diffraction analysis. FT-Raman spectroscopy measurements are consistent with a 3c–4e description of all the X−Ch−X three-body systems (Ch=Se, Te; X=Br, I) in compounds 2 , 3 , HoPyTeIIBr2 ( 5 ), and 6 . The structural and spectroscopic observations are supported by extensive theoretical calculations carried out at the DFT level that were employed to study the electronic structure of the investigated compounds, the thermodynamic aspects of their formation, and the role of noncovalent σ-hole halogen and chalcogen bonds in the X⋅⋅⋅X, X⋅⋅⋅Ch and Ch⋅⋅⋅Ch interactions evidenced structurally.
Citation
Aragoni , M C , Podda , E , Chaudhary , S , Bhasin , A K K , Bhasin , K K , Coles , S J , Orton , J B , Isaia , F , Lippolis , V , Pintus , A , Slawin , A M Z , Woollins , J D & Arca , M 2023 , ' An experimental and theoretical insight into I 2 /Br 2 oxidation of bis(pyridin‐2‐yl)diselane and ditellane ' , Chemistry-An Asian Journal , vol. 18 , no. 23 . https://doi.org/10.1002/asia.202300836
Publication
Chemistry-An Asian Journal
Status
Peer reviewed
ISSN
1861-4728Type
Journal article
Description
CINECA is kindly acknowledged for providing computational resources (ISCRA C projects BIFluoex, LithoDFT, QMPhosph). KKB is thankful to NASI for the Platinum Jubilee Fellowship and UGC - New Delhi for financial assistance.Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.