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Synthesis, Structural Characterization, Hirshfeld Analysis and AIM Analysis of 2,4,8,10-tetra-tert-butyl-6-phenyldibenzo[d,g][1,3,6,2]-dioxa-selenaphosphocine and its Oxide and Selenide Derivatives
Journal
Journal of Chemical Crystallography
ISSN
10741542
Date Issued
2023-06-01
Author(s)
Kumar, Pawan
Mondal, Dipanjan
Kunchur, Harish S.
Mague, Joel T.
Balakrishna, Maravanji S.
Abstract
The reaction of 2,2′-selenobis(4,6-di-tert-butyl phenol) with equimolar amount of dichlorophenylphosphine afforded the 8-membered cyclic phosphonite, PhP{-OC6H2(tBu)2(µ-Se)(tBu)2C6H2O-} (1). The reaction of 1 with 30% aq H2O2 resulted in the oxidation of both phosphorus and selenium to give PhP(O){-OC6H2(tBu)2(µ-Se(O))(tBu)2C6H2O-} (2) in quantitative yield. Similar reaction of 1 with one equivalent of trimethylamine-N-oxide yielded the phosphine oxide derivative, PhP(O){-OC6H2(tBu)2(µ-Se)(tBu)2C6H2O-} (3). The reaction of 1 with gray selenium in 1:1 molar ratio afforded PhP(Se){-OC6H2(tBu)2(µ-Se)(tBu)2C6H2O-} (4) in good yield. All the derivatives have been structurally characterized. Both the compounds 2 and 3 crystallized with the asymmetric unit containing a whole molecule, whereas the compound 4 crystallized with a CH2Cl2 molecule. All of these molecules showed intermolecular C−H⋅⋅⋅O and C−H⋅⋅⋅Se hydrogen bonding interactions which play major role in the crystal packing to form a three-dimensional array. Hirshfeld surface analysis, dnorm and two-dimensional fingerprint plots were investigated to validate the contributions of the different intermolecular contacts within the supramolecular structure. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of 2 are from H⋅⋅⋅H (72%), C⋅⋅⋅H/H⋅⋅⋅C (15%), O⋅⋅⋅H/H⋅⋅⋅O (10.1%) and Se⋅⋅⋅H/H⋅⋅⋅Se (2.8%) contacts, and those for 3 are from H⋅⋅⋅H (74.1%), C⋅⋅⋅H/H⋅⋅⋅C (14.2%), O⋅⋅⋅H/H⋅⋅⋅O (5.7%) and Se⋅⋅⋅H/H⋅⋅⋅Se (5.7%) contacts, while those for 4 are from H⋅⋅⋅H (75.9%), C⋅⋅⋅H/H⋅⋅⋅C (10.5%), O⋅⋅⋅H/H⋅⋅⋅O (1%) and Se⋅⋅⋅H/H⋅⋅⋅Se (12.5%) contacts. Non-covalent interactions between C–H and O were observed in the molecular structures of 2–4. These weak interactions were also assessed by DFT calculations in terms of their non-covalent interaction plots and QTAIM analysis. Graphical Abstract: This paper describes the synthesis and crystal structures of threeselenaphosphocine derivatives. The reaction of 2,2′-selenobis(4,6-di-tert-butyl phenol) with equimolar amount of dichlorophenylphosphine produce the 8-membered cyclic phosphonite 1. The reaction of 1 with 30% aq H2O2 and elemental selenium afford three different macrocyclic compounds. [Figure not available: see fulltext.]
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