Tellurium–Nitrogen π‐Heterocyclic Chemistry – Synthesis, Structure, and Reactivity Toward Halides and Pyridine of 3,4‐Dicyano‐1,2,5‐telluradiazole
Tellurium–Nitrogen π‐Heterocyclic Chemistry – Synthesis, Structure, and Reactivity Toward Halides and Pyridine of 3,4‐Dicyano‐1,2,5‐telluradiazole
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碲氮π杂环化学——3,4-二氰基-1,2,5-碲二唑的合成、结构以及对卤化物和吡啶的反应性
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
A. Zibarev
中科院分区：
文献类型：
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作者：
N. Semenov;N. Pushkarevsky;J. Beckmann;Pamela Finke;E. Lork;R. Mews;I. Bagryanskaya;Y. Gatilov;S. Konchenko;V. Vasiliev;A. Zibarev
2，3-二氨基马来腈与TeX 4的反应（X = Cl，Br）在吡啶（Py）和/或三乙胺（Et 3 N）存在下反应，得到3，4-二氰基-1，2，5-碲二唑（1），它是纯的，与吡啶、氯化物和溴化物的稳定加合物，即1·2 Py，（PyH）（1·Cl），（PyH）2（1·2Cl），（Et 3 NH）（1·Cl），（PyH）（1·Br）和（PyH）2（1·2Br）。用X射线晶体学研究了这些化合物的分子和超分子结构。在固态下，分子间通过次级Te···N相互作用以及N-H···X和N-H···N氢键（X = Cl，Br）形成缔合.用MP2计算结合分子中原子量子理论（QTAIM）和自然键轨道（NBO）分析方法研究了（PyH）（1·Br）的成键情况. 1的前线分子轨道（MO）的π对称性在1·2 Py、（1·Cl-）和（1·2Cl-）加合物中保持不变。在氯化物加合物中，最高占据分子轨道（HOMO）可以被描述为1的HOMO与氯离子的3 p原子轨道（AO）的反键组合，而最低占据分子轨道（LUMO）类似于母体1。在加合物中，电荷转移到杂环上的顺序为1·2 Py，（1·2Cl-），（1·Cl-）.在气相中的加合物的QTAIM分析揭示了封闭壳层的相互作用，而NBO分析表明负超共轭作为这些复合物的主要形成途径。这一描述与Alcock提出的重p区元素原子与具有孤对电子的原子之间的次级成键相互作用模型相一致。
The reaction of 2,3-diaminomaleonitrile with TeX4 (X = Cl, Br) in the presence of pyridine (Py) and/or triethylamine (Et3N) provided 3,4-dicyano-1,2,5-telluradiazole (1), which was isolated neat and as stable adducts with pyridine, chloride, and bromide, namely, 1·2Py, (PyH)(1·Cl), (PyH)2(1·2Cl), (Et3NH)(1·Cl), (PyH)(1·Br), and (PyH)2(1·2Br). The molecular and supramolecular structures of these compounds were investigated by X-ray crystallography. In the solid state, intermolecular associations through secondary Te···N interactions as well as N–H···X and N–H···N hydrogen bonding (X = Cl, Br) were observed. For (PyH)(1·Br), two polymorphs were found. The bonding situation of 1 and its pyridine and chloride adducts were investigated by MP2 calculations supplemented with the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. The π symmetry of the frontier molecular orbitals (MOs) of 1 are preserved in the 1·2Py, (1·Cl–), and (1·2Cl–) adducts. In the chloride adducts, the highest occupied molecular orbital (HOMO) can be described as an antibonding combination of the HOMO of 1 with the 3p atomic orbitals (AOs) of the chloride ions, whereas the lowest occupied molecular orbital (LUMO) resembles that of the parent 1. The charge transfer onto the heterocycle in the adducts increases in the order 1·2Py, (1·2Cl–), and (1·Cl–). QTAIM analyses of the adducts in the gas phase reveal closed-shell interactions, whereas NBO analyses indicate negative hyperconjugation as the main formation pathway in these complexes. This description agrees with the Alcock model suggested for secondary bonding interactions between atoms of heavy p-block elements and atoms with lone pairs.
影响因子：
2.8
作者：
J. Beckmann;Jens Bolsinger;A. Duthie;Pamela Finke
通讯作者：
J. Beckmann;Jens Bolsinger;A. Duthie;Pamela Finke
影响因子：
15
作者：
Zhang, Donghui;Ready, Joseph M.
通讯作者：
Ready, Joseph M.