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Синтез и строение бис(бромдифтор- ацетата) трис(5-бром-2-метоксифенил)висмута

Authors: Ermakova, V.A; Sharutina, O.K.;

Синтез и строение бис(бромдифтор- ацетата) трис(5-бром-2-метоксифенил)висмута

Abstract

Ермакова Валентина Андреевна – студент, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: valentinka_super.1996@bk.ru Шарутина Ольга Константиновна – доктор химических наук, профессор, заведующий кафедрой теоретической и прикладной химии, Южно-Уральский государственный университет. 454080, г. Челябинск, пр. им. В.И. Ленина, 76. E-mail: sharutinao@mail.ru. V.A. Ermakova, valentinka_super.1996@bk.ru O.K. Sharutina, sharutinao@mail.ru South Ural State University, Chelyabinsk, Russian Federation Взаимодействием трис(5-бром-2-метоксифенил)висмута с бромдифторуксусной кислотой в присутствии пероксида водорода в диэтиловом эфире (мольное соотношение 1:2:1) синтезирован бис(бромдифторацетат) трис(5-бром-2-метоксифенил)висмута (5-Br-2-MeOC6H3)3Bi[OC(O)CBrF2]2 (1), выход которого после перекристаллизации из смеси бензол-петролейный эфир составил 80 %. Использование в качестве окислителя трет-бутилгидропероксида не приводит к образованию целевого продукта. Соединение 1 охарактеризовано методом ИК-спектроскопии и рентгеноструктурного анализа. По данным РСА, в кристалле присутствуют два типа кристаллографически независимых молекул, геометрические характеристики которых незначительно отличаются. Атом висмута в молекуле имеет искаженную тригонально-бипирамидальную координацию с атомами кислорода карбоксилатных заместителей в аксиальных и атомами углерода арильных групп в экваториальных положениях. Углы между аксиальными и эк- ваториальными заместителями ОBi(1,2)O и CBi(1,2)C равны 169,3(5)°, 170,6(7)° и 113,1(8)°–123,5(8)°, 118,1(7)° – 123,1(8)°. Длины связей Bi(1,2)–O и Bi(1,2)–C состав- ляют 2,256(16), 2,276(19) Å; 2,261(14), 2,316(16) Å и 2,15(2)–2,23(2) Å; 2,18(2) –2,19(2) Å. Внутримолекулярные расстояния между валентно не связанными атомами Bi(1,2)⋅⋅⋅O(=C) (3,16(2), 3,57(4) Å; 3,11(2), 3,18(2) Å) и Bi(1,2)⋅⋅⋅OМе (3,00(2)–3,17(2) Å; 3,04(2) – 3,14(2) Å) меньше суммы ван-дер-ваальсовых радиусов атомов элементов Bi и O. Кристаллографические характеристики 1: пространственная группа P1; параметры ячейки: a = 12,775(14) Å, b = 15,999(12) Å, c = 17,196(16) Å; α = 88,09(3) град., β =68,67(5) град., γ = 87,92(4) град.; V = 3271(5) Å3. Полные таблицы координат атомов, длин связей и валентных углов депонированы в Кембриджском банке структурных данных (№ 1833279; deposit@ccdc.cam.ac.uk; http://www.ccdc. cam.ac.uk).The interaction of tris(5-bromo-2-methoxyphenyl)bismuth with bromodifluoroacetic acid in the presence of hydrogen peroxide in diethyl ether at the molar ratio (1: 2: 1) leads to the formation of tris(5-bromo-2-methoxyphenyl)bismuth bis(bromodifluoroacetate) (1) with 80 % yield after recrystallization from the benzene-petroleum ether mixture. The use of tertbutyl hydroperoxide as the oxidizing agent does not lead to the formation of the desired product. Compound 1 is characterized by IR spectroscopy and X-ray diffraction analysis. According to X-ray diffraction data, there are two types of crystallographically independent molecules in the crystal, the geometric characteristics of which differ slightly. The bismuth atom in the molecule has distorted trigonal-bipyramidal coordination with oxygen atoms of carboxylate substituents in axial positions and carbon atoms of the aryl groups at equatorial positions. The angles between the axial and equatorial substituents OBi(1,2)O and CBi(1,2)C are 169.3(5)°, 170.6(7)° and 113.1(8)° –123.5(8)°, 118.1(7)°– 123.1(8)°. The bond lengths of Bi(1,2)–O and Bi(1,2)–C are 2.256(16), 2.276(19) Å; 2.261(14), 2.316(16) Å and 2.15(2)–2.23(2) Å; 2.18(2)– 2.19(2) Å. The intramolecular distances between the valence-free nonbound atoms are Bi(1,2)⋅⋅⋅O(=C) (3.16(2), 3.57(4) Å, 3.11(2), 3.18(2) Å) and Bi(1,2)⋅⋅⋅OMe (3.00(2) – 3.17(2) Å, 3.04(2) – 3.14(2) Å) are less than the sum of the Van-der-Waals radii of Bi and O atoms. Crystallographic characteristics of 1: the space group P1; cell parameters: a = 12.775(14) Å, b = 15.999(12) Å, c = 17.196(16) Å; α = 88.09(3) degrees, β = 68.67(5) degrees, γ = 87.92 (4) degrees; V = 3271 (5) Å3. Full tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (no. 1833279; deposit@ccdc.cam.ac.uk; http: //www.ccdc. Cam.ac.uk).

Keywords

X-ray diffraction analysis, рентгеноструктурный анализ, окислительный синтез, УДК 548.312.5, oxidative synthesis, бис(бромдифторацетат) трис(5-бром-2-метоксифенил)висмута, УДК 546.87, molecular structure, молекулярная структура, УДК 547.53.024, tris(5-bromo-2-methoxyphenyl)bismuthbis(bromodifluoroacetate)

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
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