Synthesis and X-Ray Structure of the Monofunctionulized Amide-Terminated Phenylsulfide Iron(II) Clathrochelates | Sciact - CRIS-система Института катализа

Synthesis and X-Ray Structure of the Monofunctionulized Amide-Terminated Phenylsulfide Iron(II) Clathrochelates Научная публикация

Журнал

Macroheterocycles (Макрогетероциклы)
ISSN: 1998-9539

Вых. Данные

Год: 2017, Том: 10, Номер: 4-5, Страницы: 552-559 Страниц : 8 DOI: 10.6060/mhc171147v

Ключевые слова

Macrocycles, clathrochelates, cage complexes, iron complexes, ligand reactivity

Авторы

Vakarov Serhii V. ¹ , Varzatskii Оleg А. ^1,2 , Belov Alexander S. ³ , Pavlov Alexander A. ³ , Zubavichus Yan V. ⁴ , Vologzhanina Anna V. ³ , Voloshin Yan Z. ^3,5

Организации

1	Vernadskii Institute of General and Inorganic Chemistry NASU
2	SC Princeton Biomolecular Research Labs
3	Nesmeyanov Institute of Organoelement Compounds RAS
4	Kurchatov Complex for Synchrotron and Neutron Investigations, National Research Centre “Kurchatov Institute”
5	Kurnakov Institute of General and Inorganic Chemistry RAS

The monoamide-terminated cage complexes FeBd2(X-R(+)-PhCH(CH3)NHOCC6H4S)GmH)(BF)2 (where Bd2– is α-benzyldioxime dianion, Gm is glyoxime residue, X is ortho- or meta-, or para-substituent) were obtained using onepot two-step synthetic procedure that includes (i) the reaction of its monocarboxyl-terminated clathrochelate precursor with 1,1’-carbonyldiimidazole (CDI), giving the corresponding azaheterocycle-terminated intermediate, and (ii) its cleavage with R(+)-phenylethylamine leading to the target iron(II) clathrochelate with terminal optically active amide group. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass-spectrometry, IR, UV-Vis, 1H and 13C{1H} NMR spectra, and by single crystal X-ray diffraction (for a meta-substituted constitutional isomer). The number, position and integral intensities of the signals in their 1H NMR spectra confirmed the composition of the macrobicyclic molecules. The number of the signals in their 13C NMR spectra suggests the absence of the C2 symmetry axes passing through the middles of the chelate C–C bonds and of the symmetry plane also passing through these points and the encapsulated iron(II) ion as well. As follows from X-ray diffraction data, the encapsulated iron(II) ion in the molecule FeBd2((meta-R(+)-PhCH(CH3)NHOCC6H4S)GmH)(BF)2 is situated in the centre of its FeN6-coordination polyhedron with Fe–N distances falling in the range 1.8904(4)–1.9404(7) Å. This polyhedron possesses the geometry intermediate between a trigonal prism and a trigonal antiprism with the average distortion angle φ of 24.2°; its height h is equal to 2.34 Å and the average bite (chelate) angle α is approximately 78.2°. The terminal PhCH(CH3)NH group of the above clathrochelate molecule is equiprobably disordered over two sites with opposite orientation of its methyl and phenyl substituents; the N–H...F-bonded clathrochelate dimers are formed in its X-rayed crystal.

Vakarov S.V. , Varzatskii О.А. , Belov A.S. , Pavlov A.A. , Zubavichus Y.V. , Vologzhanina A.V. , Voloshin Y.Z.
Synthesis and X-Ray Structure of the Monofunctionulized Amide-Terminated Phenylsulfide Iron(II) Clathrochelates

Macroheterocycles (Макрогетероциклы). 2017. V.10. N4-5. P.552-559. DOI: 10.6060/mhc171147v WOS Scopus РИНЦ CAPlus OpenAlex

Полный текст от издателя

Поступила в редакцию:	22 нояб. 2017 г.
Принята к публикации:	10 дек. 2017 г.

Web of science:	WOS:000422743600022
Scopus:	2-s2.0-85042118244
РИНЦ:	32367974
Chemical Abstracts:	2019:1207450
OpenAlex:	W2793916606

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