Tellurium-Nitrogen p-Heterocyclic Chemistry - Synthesis, Structure, and Reactivity Toward Halides and Pyridine of 3,4-Dicyano-1,2,5-telluradiazole

Tellurium-Nitrogen p-Heterocyclic Chemistry - Synthesis, Structure, and Reactivity Toward Halides and Pyridine of 3,4-Dicyano-1,2,5-telluradiazole Научная публикация

Журнал

European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682

Вых. Данные

Год: 2012, Номер: 23, Страницы: 3693-3703 Страниц : 11 DOI: 10.1002/ejic.201200376

Ключевые слова

Computational chemistry; Tellurium; Nitrogen heterocycles

Авторы

Semenov Nikolay A. ² , Pushkarevsky Nikolay A. ³ , Beckmann Jens ¹ , Finke Pamela ¹ , Lork Enno ¹ , Mews Ruediger ¹ , Bagryanskaya Irina Yu. ² , Gatilov Yuri V. ² , Konchenko Sergey N. ³ , Vasiliev Vladimir G. ² , Zibarev Andrey V. ^2,4

Организации

1	(Данные Web of science) Univ Bremen, Inst Inorgan & Phys Chem, D-28334 Bremen, Germany
2	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Inst Inorgan Chem, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Phys, Novosibirsk 630090, Russia

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 NH...X and NH...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 p 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.

Semenov N.A. , Pushkarevsky N.A. , Beckmann J. , Finke P. , Lork E. , Mews R. , Bagryanskaya I.Y. , Gatilov Y.V. , Konchenko S.N. , Vasiliev V.G. , Zibarev A.V.
Tellurium-Nitrogen p-Heterocyclic Chemistry - Synthesis, Structure, and Reactivity Toward Halides and Pyridine of 3,4-Dicyano-1,2,5-telluradiazole
European Journal of Inorganic Chemistry. 2012. N23. P.3693-3703. DOI: 10.1002/ejic.201200376 WOS Scopus РИНЦ

Опубликована online:	5 июл. 2012 г.
Опубликована в печати:	1 авг. 2012 г.

Web of science	WOS:000307222000004
Scopus	2-s2.0-84864706021
РИНЦ	20492615
OpenAlex	W2055518328