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, d_norm 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 three selenaphosphocine 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.

中文翻译：

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2,4,8,10-四叔丁基-6-苯基二苯并[d,g][1,3,6,2]-dioxa-selenaphosocine及其氧化物的合成、结构表征、Hirshfeld分析和AIM分析硒化物衍生物

2,2'-硒双(4,6-二叔丁基苯酚)与等摩尔二氯苯基膦反应得到8元环亚膦酸酯PhP{-OC ₆ H ₂ ( ^t Bu) ₂ ( µ -Se )( ^tBu ) ₂ C ₆ H ₂ O - } ( 1 ). 1与 30% 含水 H ₂ O ₂的反应导致磷和硒氧化，生成 PhP(O){-OC ₆ H ₂ ( ^t Bu) ₂ ( µ -Se(O))(^t Bu) ₂ C ₆ H ₂ O - } ( 2 ) 定量产率。1与一当量三甲胺-N-氧化物的类似反应产生氧化膦衍生物 PhP(O){-OC ₆ H ₂ ( ^t Bu) ₂ ( µ -Se)( ^t Bu) ₂ C ₆ H ₂ O - } ( 3 ). 1与灰色硒以1:1的摩尔比反应得到PhP(Se){-OC ₆ H ₂ ( ^tBu) ₂ ( µ -Se)( ^t Bu) ₂ C ₆ H ₂ O - } ( 4 ) 收率高。所有衍生物都已进行结构表征。化合物2和3均以包含完整分子的不对称单元结晶，而化合物4以 CH ₂ Cl ₂分子结晶。所有这些分子都显示出分子间 C−H⋅⋅⋅O 和 C−H⋅⋅⋅Se 氢键相互作用，它们在晶体堆积形成三维阵列中起主要作用。Hirshfeld 表面分析，d_范数研究了二维指纹图，以验证超分子结构内不同分子间接触的贡献。Hirshfeld 表面分析表明，对2的晶体堆积最重要的贡献来自 H⋅⋅⋅H（72%）、C⋅⋅⋅H/H⋅⋅⋅C（15%）、O⋅⋅⋅H/ H···O (10.1%) 和 Se···H/H···Se (2.8%) 接触，3的接触来自 H···H (74.1%)，C···H/H ⋅⋅⋅C (14.2%), O⋅⋅⋅H/H⋅⋅⋅O (5.7%) 和 Se⋅⋅⋅H/H⋅⋅⋅Se (5.7%) 接触，而4个来自 H⋅ ⋅⋅H（75.9%），C⋅⋅⋅H/H⋅⋅⋅C（10.5%），O⋅⋅⋅H/H⋅⋅⋅O（1%）和 Se⋅⋅⋅H/H⋅⋅⋅ Se (12.5%) 触点。在2 – 4的分子结构中观察到 C–H 和 O 之间的非共价相互作用. 这些弱相互作用也通过 DFT 计算根据非共价相互作用图和 QTAIM 分析进行了评估。

图形概要

本文介绍了三种硒代磷酸衍生物的合成和晶体结构。2,2'-硒双(4,6-二叔丁基苯酚)与等摩尔二氯苯基膦反应生成8元环亚膦酸酯1。1与 30% aq H ₂ O ₂和元素硒的反应提供了三种不同的大环化合物。