Interaction of organyltriphenylphosphonium halides with potassium dihalogenodicyanoaurates in water followed by recrystallization of reaction products from acetonitrile or DMSO has been used to synthesize gold(III) ionic complexes [Ph3PMe][Au(CN)2Cl2] (1), [Ph3PCH2Ph][Au(CN)2Cl2] (2), [Ph3PC6H11-cyclo][Au(CN)2Br2] (3), and [Ph4P][Au(CN)2I2] (4), which have been structurally characterized by the X-ray analysis method (CIF files CCDC No. 1901681 (1), 1912903 (2), 1912919 (3), 2048146 (4)). According to the X-ray data crystals 1–4 consist of centrosymmetric square-planar [Au(CN)2Hal2]– anions (the Au–Hal average bond lengths are 2.417(3) Å (1), 2.280(2) Å (2), 2.4203(13) Å (3), and 2.6035(10) Å (4); the Au–C average bond lengths are 2.06(2) Å (1), 2.010(7) Å (2), 2.009(7) Å (3,) and 1.998(6) Å (4)); the phosphorus atoms in organyltriphenylphosphonium cations have a slightly distorted tetrahedral coordination (the P–C bond lengths are 1.782(9)-1.806(8) Å (1), 1.788(4)-1.813(5) Å (2), 1.790(5)-1.813(5) Å (3) and 1.793(6)-1.799(5) Å (4)). The structural organization in crystals 2–4 is caused by the interionic С–H∙∙∙N≡C hydrogen bonds (C–HPh∙∙∙N≡C 2.56 Å (2); C–HPh∙∙∙N≡C 2.43–2.59 Å, C–Hcyclohexyl∙∙∙N≡C 2.47 Å (3), C–HPh∙∙∙N≡C 2.63 Å (4)), while in crystals 1 no significant interionic contacts are observed.
Южно-Уральский государственный университет, г. Челябинск, Россия Взаимодействием галогенидов тетраорганилфосфония с дихлоро-, дибромо-и дииододицианоауратом калия в воде с последующей перекристаллизацией из ацетонитрила синтезированы ионные комплексы золота(III) [Me 4 P][Au(CN) 2 Cl 2 ] (1), [Ph 3 PR][Au(CN) 2 Hal 2 ] (Hal = Cl, R = (CH 2 ) 6 Me (2), (CH 2 ) 2 C(O)OH (3); Hal = Br, R = CH 2 CN (4); Hal = I, R = CH 2 CN (5)) и [Ph 3 PCH=CHPPh 3 ][Au(CN) 2 Cl 2 ] 2 (6). Аналогичным путем взаимодействием хлорида тетрафенилстибония с дихлородицианоауратом калия получен комплекс [Ph 4 Sb][Au(CN) 2 Cl 2 ] (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 (
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