Archive for 30.11.2015

Tetrahedron Lett., 2015, 7020-7023

A.D. Lisakova, D.S. Ryabukhin, R.E. Trifonov, V.A. Ostrovskii, A.V. Vasilyev

“Alkylation of 5-substituted NH-tetrazoles by alcohols in the superacid CF3SO3H”

Tetrahedron Lett., 2015, 56, 7020-7023

Reactions of 5-substituted NH-tetrazoles with alcohols in the superacid CF3SO3H have been studied. Both the structure of the tetrazole and the nature of alcohol were found to dramatically influence the selectivity of the reaction and yields of products. Tetrazoles bearing phenyl, electron-donating aryl, or benzyl groups at the 5-position, have been alkylated using various alcohols (including MeOH and EtOH) in CF3SO3H upon heating at 60 °C for 0.3–12 h to afford 2-alkyl-2H-tetrazoles in 30–98% yields.

Журнал Структурной Химии, 2015, 937-944

Е.А. Катленок, А.А. Золотарев, А.Ю. Иванов, С.Н. Смирнов, К.П. Балашев

“Строение, оптические и электрохимические свойства биядерных комплексов с платинированным 2-фенилбензотиазолом, и мостиковыми 2-меркапто-производными пиридина, пиримидина, бензотиазола и бензоксазола”

Журнал Структурной Химии, 2015, 56(5), 937-944
DOI: 10.15372/JSC20150509

Биядерные комплексы [Pt(bt)-(N^S)](bt — депротонированная форма 2-фенилбензотиазола, (N^S) = 2-меркаптопиридинат, 2-меркаптопиримидинат, 2-меркаптобензотиазолат, 2-меркаптобензоксазолат ионы) охарактеризованы следующими методами: РСА, ЯМР 1H и 195Pt спектроскопии, электронной спектроскопии поглощения и испускания, циклической вольтамперометрии. Показано наличие химической связи Pt — Pt и существование комплексов как в кристаллическом состоянии, так и в растворе в виде цис-N(bt),S-связевых изомеров с ассиметричным расположением двух двух циклометаллированных двух мостиковых лигандов. Длинноволновые полосы поглощения и люминесценция комплексов в красной области спектра обусловлены спин-разрешенным и спин-запрещенным оптическим переходом переноса заряда со связи металл-металл на металлированный лиганд. В циклической вольтамперометрии двухэлектронные волны окисления и восстановления комплексов отнесены к металл- и лиганд-центрированным процессам с участием σ*-ВЗМО и π*(bt)-НСМО комплексов.

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Spinus 2015, А. А. Шмырева

Доклад сотрудника РЦ Анны Шмырева на конференции Spinus 2015. «Nuclear magnetic resonance study of Ni nanoparticles». Видео версию доклада можно посмотреть тут

Spinus 2015, А. С. Мазур

Доклад нашего коллеги Антона Мазура на конференции Spinus 2015 «Применение метода ЯМР для исследования свойств магнито-упорядоченных веществ». Видео версию доклада можно посмотреть тут.

Green Chemistry, 2015

K.S. Rodygin, V.P. Ananikov

“An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source”

Green Chemistry, 2015, accepted

Chemical reactions involving high-pressure acetylene are not easily performed in a standard laboratory setup. The risk of explosion and technical difficulties drastically complicate the equipment and greatly increase the cost. In this study, we propose the replacement of acetylene with calcium carbide, which was successfully utilized to synthesize practically useful vinyl thioesters in accordance with a simple and environmentally benign procedure. The reaction proceeded under mild conditions using a standard laboratory setup. The optimized reaction conditions allowed the selective synthesis of the vinyl thioesters in high yields, and the reaction conditions can be scaled up to synthesize grams of sulfides from inexpensive starting materials.

Russ. J. Org. Chem., 2015, 640-643

A.P. Molchanov, E.V. Sirotkina, M.M. Efremova, R.R. Kostikov, A.V. Ivanov, V.S. Shcherbakova

“Regio- and Stereoive Cycloaddition of Nitrones to 1-Vinyl-4,5-dihydro-1Н-benzo[g]indole”

Russ. J. Org. Chem., 2015, 51, 640-643

Nitrones cycloaddition to 1-vinyl-4,5-dihydro-1Н-benzo[g]indole proceeds regio- and steroselectively affording a single diastereomer of 5-(hetaryl-substituted)isoxazolidine.

J. Molec. Struct., 2015, 169-173

I.S. Ignatyev, T.A. Kochina, V.V. Avrorin, V.V. Gurzha, I.M. Fundamensky

“Molecular and crystal structure of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane”

J. Molec. Struct., 2015, 1094, 169-173

The crystal structure of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane [HPhSi(OCH2CH2)2NMe – phenylhydrosilocane (I)] is determined by single-crystal X-ray diffraction at 100 K. The unit cell consists of four molecules connected only by Van-der-Waals interactions. Each molecule has an eight-membered heterocycle with a phenyl group in the axial position. The Si⋯N transannular bond has a short (2.206 Å) interatomic distance which exceeds only this distance in ocanes with highly electronegative fluorine substituents at Si. Since there exist experimental data on the occurrence of different conformers of I in the liquid phase, the PES of the molecule was analyzed by DFT B3LYP and MP2 methods with the aug-cc-pVDZ basis set. The energy minimum belongs to the boat–chair conformation with the axial position of the phenyl group. Rotation of the phenyl ring around the SiC bond has a barrier ca. 1 kcal/mol. The conformer with the equatorial position of this group lies 6 kcal/mol higher. Interconversion of this conformers which was observed in experiment proceeds through the chair–chair configuration in which the Si⋯N transannular bond is absent and coordination at silicon is tetrahedral, rather than trigonal bipyramidal one observed in other conformers.

Angew. Chem. Int. Ed., 2015, 1-6

S.N. Britvin, S.A. Kashtanov, M.G. Krzhizhanovskaya, A.A. Gurinov, O.V. Glumov, S. Strekopytov, Yu.L. Kretser, A.N. Zaitsev, N.V. Chukanov, S.V. Krivovichev

“Perovskites with the Framework-Forming Xenon”

Angew. Chem. Int. Ed., 2015, 54, 1-6

The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO6) (M=Ca, Sr, Ba) containing framework-forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner-sharing (XeO6) and (NaO6) octahedra arranged in a three-dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated XeVIII and SiIV exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that XeVIII can be incorporated into hyperbaric frameworks such as MgSiO3 perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas.

Tetrahedron, 2015, 7931-7937

D.V. Kurandina, E.V. Eliseenkov, T.S. Khaibulova, A.A. Petrov, V.P. Boyarskiy

“Copper-catalyzed C-N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived oxalyl dihydrazide: scope and limitation”

Tetrahedron, 2015, 71, 7931-7937


An efficient and convenient method has been developed for the copper-catalyzed C–N bond cross-coupling of aryl bromides with electron-donor substituents and aliphatic amines in water. The new ligand system N-phenyloxalyl bishydrazide/hexane-2,5-dione has been shown to be considerably more efficient in the copper-catalyzed C–N bond cross-coupling reaction as compared to the ligands described in the literature and allowed decreasing of the catalyst amount (up to 2 mol %) to achieve acceptable yields of isolated products (46–84%). Acceptor substituted aryl bromides, aryl bromides with substituents in the ortho-position, and some aryl dichlorides can undergo the C–N cross-coupling under the developed conditions, but their reactivity is lower.