Синтез и строение новых дигалогендицианоауратных комплексов
Автор: Шевченко Дмитрий Павлович, Хабина Анастасия Евгеньевна, Сенчурин Владислав Станиславович
Журнал: Вестник Южно-Уральского государственного университета. Серия: Химия @vestnik-susu-chemistry
Рубрика: Химия элементоорганических соединений
Статья в выпуске: 1 т.12, 2020 года.
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Взаимодействием галогенидов тетраорганилфосфония с дихлоро-, дибромо- и дииододицианоауратом калия в воде с последующей перекристаллизацией из ацетонитрила синтезированы ионные комплексы золота(III) [Me4P][Au(CN)2Cl2] (1), [Ph3PR][Au(CN)2Hal2] (Hal = Cl, R = (CH2)6Me (2), (CH2)2C(O)OH (3); Hal = Br, R = CH2CN (4); Hal = I, R = CH2CN (5)) и [Ph3PCH=CHPPh3][Au(CN)2Cl2]2 (6). Аналогичным путем взаимодействием хлорида тетрафенилстибония с дихлородицианоауратом калия получен комплекс [Ph4Sb][Au(CN)2Cl2] (7). Строение комплексов 3, 5-7 установлено методом рентгеноструктурного анализа (РСА). По данным РСА, атомы фосфора и сурьмы в 3, 5-7 имеют искаженную тетраэдрическую координацию (углы СPС 107,5(2)-111,8(3)° (3), 106,0(3)-111,5(3)° (5), 106,7(4)-111,8(4)° (6), CSbC 100,5(7)-114,6(5)° (7); длины связей P-С 1,788(5)-1,807(5) Å (3), 1,765(6)-1,821(6) Å (5), 1,781(8)-1,810(8) Å (6); Sb-C 2,070(11)-2,121(12) Å (7)). Атомы золота в анионах [Au(CN)2Hal2]- имеют малоискаженную плоскоквадратную координацию ( транс -углы HalAuHal и CAuC близки к 180°; цис -углы CAuHal изменяются в интервале 88,05-92,48°), длины связей Au-Hal составляют: Au-Cl 2,328(3) Å (3), 2,393(2), 2,411(2) Å (6), 2,4223(12) Å (7); Au-I 2,609(3), 2,598(3) Å (5), Au-C - 1,981(7) Å (3), 1,996(7), 2,006(8) Å (5), 1,978(12), 2,001(13) Å (6), 2,040(15) (7). Структурная организация в кристаллах 3, 5-7 обусловлена нековалентными взаимодействиями различной природы: С-H∙∙∙N≡C 2,55-2,74 Å (3, 5-7), O-H∙∙∙N≡C 2,03 Å, С-H∙∙∙O=C 2,52 Å, C-H∙∙∙Cl-Au 2,88-2,93 Å (3), Au-I∙∙∙I-Au 3,925(4) Å (5), C-H∙∙∙Cl-Au 2,91 Å (6).
Дигалогендицианоаурат калия, галогениды тетраорганилфосфония, хлорид тетрафенилстибония, синтез, строение, рентгеноструктурный анализ
Короткий адрес: https://sciup.org/147233153
IDR: 147233153 | DOI: 10.14529/chem200103
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