English

«МРТ взгляд» на процесс электролиза


МРТ изображения (спектрометр Bruker 400 WB Avance III) электрохимической ячейки, заполненной водным раствором хлорида железа (II), при различных напряжениях.

Химический турнир


13–19 марта в СПбГУ проходит «Всероссийский химический турнир школьников». Для начинающих химиков, участников данного турнира, в РЦ МРМИ проведена обзорная экскурсия-лекция, посвященная магнитно-резонансным методам исследования.

New J. Chem., 2017, 41, 316-325

Elena V. Andrusenko, Evgeniy V. Kabin, Alexander S. Novikov, Nadezhda A. Bokach, Galina L. Starova and Vadim Yu. Kukushkin

“Metal-mediated generation of triazapentadienate-terminated di- and trinuclear μ2-pyrazolate NiII species and control of their nuclearity”

New J. Chem., 2017, 41, 316-325
DOI:10.1039/C6NJ02962K
источник: http://pubs.rsc.org/

1,3,5-Triazapentadienate-terminated di- and trinuclear nickel(II) complexes featuring bridging azolate ligands, [Ni2(μ2-azolate)2(TAP)2] (TAP = H[N with combining low line][double bond, length as m-dash]C(OMe)NC(OMe)[double bond, length as m-dash][N with combining low line]H; azole = 3,5-Me2pyrazole 2, 3,5-Ph2pyrazole 3) and [Ni3(μ2-azolate)4(TAP)2] (azole = 3,5-Me2pyrazole 4, indazole 5), were obtained from systems Ni2+/NCNR2/azole systems in MeOH. The terminal TAP ligands in the [Ni2(μ2-azolate)2(TAP)2] and [Ni3(μ2-azolate)4(TAP)2] species originate from the previously unreported cascade NiII-mediated and chelation-driven reaction between cyanamides and methanol. The oligomeric species and also [Ni(TAP)2] (1) are subject to interconversions that depend on the reactants involved and the reaction conditions. The control of the nuclearity of the complexes can be achieved by changing the amount of azoles or by their protonation, alteration of the steric hindrance of the substituents in the heterocycles, and by changing the reaction temperature. Complexes 1–4 were characterized using elemental (C, H, N) analyses, 1H, 13C{1H} NMR, FTIR, HRESI-MS, TG-DTA, X-ray crystallography, and 5 was characterized using HRESI-MS and X-ray crystallography. Unconventional metallophilic contacts NiII⋯NiII were observed in dimer 3 in the solid state (the distance for Ni⋯Ni is 2.99 Å, whereas the double Bondi’s vdW radius for Ni is 3.26 Å) and the reality of these interactions was confirmed theoretically by the topological analysis of the electron density distribution (AIM method). The estimated energy for these non-covalent Ni⋯Ni interactions (ca. 4 kcal mol−1) fills the gap in the reported energies of the metal⋯metal interactions in a series comprising of NiII⋯NiII (this work), PdII⋯PdII (4.3–6.0 kcal mol−1), and PtII⋯PtII (3.9–11.7 kcal mol−1).

 

Подводная «мухоловка»

источник: http://oceanexplorer.noaa.gov/okeanos/explorations/ex1702/dailyupdates/media/video/dive07_anemone/anemone.htmlВид актинии, который по форме и способу охоты схож с хищным растением венерина мухоловка. Обнаружена эта актиния в ходе экспедиции Национального управления океанических и атмосферных исследований по исследованию морского дна в районе архипелага Самоа в южной части Тихого океана (National Oceanic and Atmospheric Administration office of ocean exploration and research, корабль «Okeanos Explorer»). Видео с этим «цветком» можно найти в видеоматериалах экспедиции 2017 American Samoa

Экскурсия

Сегодня РЦ МРМИ посетили преподаватели и студенты Санкт-Петербургского государственного технологического института. Михаил Вовк провел демонстрацию оборудования и рассказал об основных задачах, решаемых в РЦ.

Февраль

В феврале выполнена  1781 заявка на сервисные измерения.

Измерено:

  • 1635 спектров 1H
  • 294 спектра 13C
  • 162 спектра DEPT
  • 38 спектров COSY
  • 15 спектров NOESY
  • 37 спектров 31Р
  • 80 спектров 19F

Выполнено 199 заявок на исследовательскую работу.

Inorganica Chimica Acta, 2017, 455, 607–612

Mikhail A. Kinzhalov, Galina L. Starova, Vadim P. Boyarskiy

“Interaction of benzene-1,2-diamines with isocyanide complexes of palladium(II): Insight into the mechanism”

Inorganica Chimica Acta, 2017, 455, 607–612
DOI:10.1016/j.ica.2016.05.014
источник: http://www.sciencedirect.com/science/article/pii/S0020169316302432

Reactivity of 4-toluidine (2) and 4,5-dimethylbenzene-1,2-diamine (3) were compared in coupling with the palladium-bis(isocyanide) complex cis-[PdCl2(CNXyl)2] (Xyl = 2,6-Me2C6H3, 1), mixed isocyanide/diaminocarbene species cis-[PdCl2(CNXyl){C(NHXyl)double bond; length as m-dashNH(4-C6H4CH3)}] (4), and cis-[PdCl(CNXyl){C(NHXyl)double bond; length as m-dashNHC6H2(Me)2NH2}]Cl (5). In these Pd(II)-mediated reactions, 4,5-dimethylbenzene-1,2-diamine (3) was significantly more reactive than 4-toluidine (2), leading to the first mixed bis(diaminocarbene) complex cis-[PdCl{C(NHR)double bond; length as m-dashNHC6H2X2NH2}{C(NHXyl)double bond; length as m-dashNH(4-C6H4CH3)}]Cl (6) containing two different diaminocarbene ligands. Complex 6 was isolated and characterized by elemental analyses (C, H, N), HRESI+-MS, IR, 1H and 13C{1H} NMR spectroscopies, and single-crystal X-ray diffraction.

 

Конференция

Институт химии растворов им. Г.А. Крестова РАН приглашает молодых научных сотрудников, аспирантов, а также студентов старших курсов принять активное участие в работе XI Всероссийской школе-конференции молодых ученых «Теоретическая и экспериментальная химия жидкофазных систем» (Крестовские чтения), которая пройдет с 30 октября по 4 ноября 2017 г. в г. Иваново. Первый циркуляр.

Секция 1. Физико-химические методы исследования жидкофазных растворов
   1.1. Теория и моделирования жидкофазных растворов (Молекулярная динамика, Монте-Карло, Квантовая химия, методы статистической термодинамики)
   1.2. Методы молекулярной спектроскопии в исследовании биологических и фармацевтических сред.
   1.3. Электрохимия растворов и расплавов солей
Секция 2. Супрамолекулярная химия и наноматериалы
   2.1. Макрогетероциклические соединения и новые материалы на их основе.
   2.2. Полимерные нанокомпозитные материалы: технологии получения и модификации.
   2.3. Золь-гель технологии для получения современных наноматериалов.
   2.4. Технологии получения супрамолекулярных систем на основе лекарственных соединений.
   2.5. Сверхкритические технологии получения наноматериалов

Glass Phys Chem, 2017, 43, 70–74

V.V. Tomaev, A.S. Mazur, A.S. Grevtsev

“A study of the process of thermal oxidation of lead selenide by the NMR and XRD methods”

Glass Phys. Chem., 2017, 43, 70–74
DOI:10.1134/S1087659617010163

Studies of the process of oxidation of powder samples of lead selenide in a dry air atmosphere have been performed. As shown by the methods of X-ray diffraction and scanning electron microscopy, the process of thermal treatment of samples resulted in the formation of the PbSeO3 phase, aside from the initial PbSe phase. Studies by the method of nuclear magnetic response (NMR) allowed revealing the dynamics of changes in the spectrum under the changed thermal treatment conditions.

 

Eur. J. Mineral., 2016, 28, 931–941

T.L. Panikorovskii, S.V. Krivovichev, E.V. Galuskin, V.V. Shilovskikh, A.S. Mazur, A.V. Bazai

“Si-deficient, OH-substituted, boron-bearing vesuvianite from Sakha-Yakutia, Russia: a combined single-crystal, 1H MAS-NMR and IR spectroscopic study”

Eur. J. Mineral., 2016, 28, 931–941
DOI:10.1127/ejm/2016/0028-2570

источник: http://www.ingentaconnect.com/content/schweiz/ejm/2016/00000028/00000005/art00006

Single crystals of Si-deficient vesuvianite with significant degree of hydrogarnet-type (SiO4)4−–(O4 H4)4− substitution occur as epitactic overgrowth on the surface of large wiluite crystals from the Wiluy River, Sakha–Yakutia, Russia. Electron-microprobe analysis revealed considerable Si-deficiency, Si ranging from 16.30 to 17.50 apfu. The crystal structure of the mineral has been refined in the P4/nnc space group, a = 15.5876(4), b = 11.8021(5) Å to R 1 = 0.028 for 1533 unique observed reflections. The refinement of the site-occupancy factors confirmed significant vacancy at the Z(1) and Z(2) sites (27% and 10%, respectively), with associated increase of the Z(1)–O and Z(2)–O bond lengths to 1.697 and 1.655 Å, respectively. The increased size of the Z(1) tetrahedra results in the compression of the X(1) polyhedra, while the expansion of the Z(2) tetrahedra is compensated by the compression of the X(4) polyhedra. As a result, the significant degree of the hydrogarnet-type substitutions does not have an essential influence upon the unit-cell parameters compared to the usual defect-free vesuvianite. Thermogravimetric (TGA) and differential scanning calorimetry (DSC) curves indicated two steps of the weight loss in the temperature ranges of 600–900°C (2.08 wt%) and 1014°C (2.22 wt%). The total weight loss is estimated as 4.30%, which is in good agreement with the total content of OH estimated as 13.72 apfu. The 1H solid state MAS-NMR demonstrates the presence of a strong additional line at 3.38 ppm compared to the usual vesuvianite, which is explained by the existence of the additional H(3) site. The infrared spectrum in the OH-stretching vibration region shows the additional (B′) absorption band at 3618 cm−1 typical for a hydrogarnet-type substitution.