Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory

Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory Научная публикация

Журнал

Organometallics
ISSN: 0276-7333

Вых. Данные

Год: 2014, Том: 33, Номер: 16, Страницы: 4302-4314 Страниц : DOI: 10.1021/om5006403

Авторы

Semenov Nikolay A. ¹ , Lonchakov Anton V. ^2,4 , Pushkarevsky Nikolay A. ^3,5 , Suturina Elizaveta A. ^2,4 , Korolev Valery V. ² , Lork Enno ⁶ , Vasiliev Vladimir G. ¹ , Konchenko Sergey N. ^3,5 , Beckmann Jens ⁶ , Gritsan Nina P. ^2,4 , Zibarev Andrey V. ^1,4,7

Организации

1	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, 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
5	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Nat Sci, Novosibirsk 630090, Russia
6	(Данные Web of science) Univ Bremen, Inst Inorgan Chem, D-28359 Bremen, Germany
7	(Данные Web of science) Tomsk State Univ, Natl Res Univ, Dept Chem, Tomsk 634050, Russia

New products of coordination of anions X- (X = F, I, PhS) to the Te atom of 3,4-dicyano-1,2,5-telluradiazole (1) were synthesized in high yields and characterized by X-ray diffraction (XRD) as the salts [(Me2N)(3)Sr+[1-F](-) (9), [K(18-crown-6)](+) [1-I](-) (10), and [K(18-crown-6)](+)[1-SPh](+)center dot THF (11), respectively. In the crystal lattice of 10, I atoms are bridging between two Te atoms. The bonding situation in anions of the salts 9-11 and some other adducts of 1,2,5-chalcogenadiazoles (chalcogen = S, Se, Te) and anions X- (X = F, Cl, Br, I, PhS) was studied using DFT, QTAIM, and NBO calculations, for 9-11 in combination with UV-vis, IR/Raman, and MS-ESI techniques. In all cases, the nature of the coordinate bond is negative hyperconjugation involving the transfer of electron density from X- to the heterocycles. The energy of the bonding interaction varies in a range from similar to 30 kcal mol(-1) comparable with energies of weak chemical bonds (e.g., internal N-N bond in organic azides) to similar to 86 kcal mol(-1) comparable with an energy of the C-C covalent bonds. The thermodynamics of the anions' coordination to 1 and their Se and S congeners was also studied by quantum chemical calculations. The general character of this reaction and favorable thermodynamics in the case of heavier chalcogens (Se, Te) were established. Comparison with available data on acyclic analogues, i.e. the chalcogen diimines RN=X=NR, reveals that they also coordinate various anions but in addition reactions across X=N (X = S, Se, Te) double bonds. Attempts to prepare the anion [1-TePh](-) led to disintegration of 1. The only unambiguously identified product was a rather rare tellurocyanate that was characterized by XRD and elemental analysis as the salt [K(18-crown-6)](+)[TeCN](-) (13).

Semenov N.A. , Lonchakov A.V. , Pushkarevsky N.A. , Suturina E.A. , Korolev V.V. , Lork E. , Vasiliev V.G. , Konchenko S.N. , Beckmann J. , Gritsan N.P. , Zibarev A.V.
Coordination of Halide and Chalcogenolate Anions to Heavier 1,2,5-Chalcogenadiazoles: Experiment and Theory
Organometallics. 2014. V.33. N16. P.4302-4314. DOI: 10.1021/om5006403 WOS Scopus

Опубликована online:	5 авг. 2014 г.
Опубликована в печати:	25 авг. 2014 г.

Web of science	WOS:000340861600019
Scopus	2-s2.0-84906568954
OpenAlex	W2323932129