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The reactions of potassium dichlorodicyanoaurate with n-propyl-, iso-butyl-, and n-heptyltriphenylphosphonium bromides in water followed by recrystallization from acetonitrile give dichlorodicyanoaurate complexes [Ph3P(n-Pr)][Au(CN)2Cl2] (I), [Ph3P(i‑Bu)][Au(CN)2Cl2] (II), and [Ph3P(n-Hp)][Au(CN)2Cl2] (III). Compounds I−III are identified by elemental analysis and IR spectroscopy. The structure of compound III is also proved by X-ray diffraction (XRD) (CIF file CCDC no. 2094701). According to the XRD data, complex III consists of n-heptyltriphenylphosphonium cations and crystallographically independent planar square dichlorodicyanoaurate anions of two types with similar geometric parameters. The steric organization of the crystal of complex III is formed by hydrogen bonds С–H∙∙∙N≡C (2.55–2.63 Å) and С–H∙∙∙Cl–Au (2.87 Å). In addition, the structure contains С–H∙∙∙π(Ph) contacts with the distances from the hydrogen atom to the benzene ring plane equal to 2.80 Å. [ABSTRACT FROM AUTHOR]

The reactions of potassium dichloro- and dibromodicyanoaurate with appropriate ethyl and (2‑bromoethyl)triphenylphosphonium halides in water gave new dihalodicyanoaurate complexes [Ph3PE-t][Au(CN)2Cl2] (I) and [Ph3PCH2CH2Br][Au(CN)2Br2] (II), which were characterized by X-ray diffraction (CCDC nos. 1963511 (I) and 2060274 (II)). According to X-ray diffraction data, complexes I and II consist of tetrahedral organyltriphenylphosphonium cations and two types of crystallographically independent square planar dihalodicyanoaurate anions with similar geometric parameters. The phosphorus atoms in the phosphonium cations have a slightly distorted tetrahedral coordination. The centrosymmetric crystallographically independent anions [Au(CN)2Cl2]– in I have a nearly undistorted square planar geometry, whereas the geometry of the [Au(CN)2Br2]– anions in II is substantially distorted (the CAuBr cis-angles vary in the range of 74.5(9)°–105.5(9)°). The spatial organization in the crystals of I and II is formed by the C–H∙∙∙N≡C hydrogen bonds and, in the case of complex II, also by additional inter-ion C–H∙∙∙Br–Au contacts. [ABSTRACT FROM AUTHOR]

The reactions of potassium dichloro- and dibromodicyanoaurate with appropriate ethyl and (2‑bromoethyl)triphenylphosphonium halides in water gave new dihalodicyanoaurate complexes [Ph3PE-t][Au(CN)2Cl2] (I) and [Ph3PCH2CH2Br][Au(CN)2Br2] (II), which were characterized by X-ray diffraction (CCDC nos. 1963511 (I) and 2060274 (II)). According to X-ray diffraction data, complexes I and II consist of tetrahedral organyltriphenylphosphonium cations and two types of crystallographically independent square planar dihalodicyanoaurate anions with similar geometric parameters. The phosphorus atoms in the phosphonium cations have a slightly distorted tetrahedral coordination. The centrosymmetric crystallographically independent anions [Au(CN)2Cl2]– in I have a nearly undistorted square planar geometry, whereas the geometry of the [Au(CN)2Br2]– anions in II is substantially distorted (the CAuBr cis-angles vary in the range of 74.5(9)°–105.5(9)°). The spatial organization in the crystals of I and II is formed by the C–H∙∙∙N≡C hydrogen bonds and, in the case of complex II, also by additional inter-ion C–H∙∙∙Br–Au contacts. [ABSTRACT FROM AUTHOR]

Ionic gold(III) complexes [Ph3PMe][Au(CN)2Cl2] (I), [Ph3PCH2Ph][Au(CN)2Cl2] (II), [Ph3PC6H11-cyclo][Au(CN)2Br2] (III), and [Ph4P][Au(CN)2I2] (IV) are synthesized by the reactions of organyltriphenylphosphonium halides with the corresponding potassium dihalodicyanoaurates in water followed by the recrystallization of the reaction products from acetonitrile or DMSO. The complexes are characterized by X-ray diffraction (XRD) (CIF files CCDC nos. 1901681 (I), 1912903 (II), 1912919 (III), and 2048146 (IV)) and IR spectroscopy. According to the XRD data, the crystals of complexes I–IV consist of centrosymmetric square-planar anions [Au(CN)2Hal2]– and organyltriphenylphosphonium cations with a slightly distorted tetrahedral coordination of the phosphorus atoms. The structural organization in the crystals of complexes II–IV is formed by interionic hydrogen bonds С–H∙∙∙N≡C, whereas no significant interionic contacts are observed in the crystals of complex I. [ABSTRACT FROM AUTHOR]

The ionic complexes [Ph3PR][Au(CN)2Cl2] (R = CH2CH=CHCH3 (I), CH2CN (II)) were prepared by the reactions of organyltriphenylphosphonium chlorides with potassium dichlorodicyanoaurate in water followed by recrystallization from acetonitrile. Apart from the major product II, the crystals of the molecular complex Ph3PC(H)(CN)Au(CN)2Cl (III) were isolated. The products were characterized by X-ray diffraction (CIF files CCDC nos. 1957185 (I), 2060227 (II), 2066549 (III)) and NMR and IR spectroscopy. According to X-ray diffraction data, complexes I and II consisted of organyltriphenylphosphonium cations with a slightly distorted tetrahedral geometry of phosphorus atoms and the centrosymmetric square anions [Au(CN)2Cl2]−, which, in the case of complex II, form coordination pseudopolymer chains via the Au∙∙∙Cl interanion contacts (3.40 Å). In complex III, the phosphorus and gold atoms are also coordinated in the tetrahedral and square environments; the ylide carbon atom is located at the gold atom in the trans-position relative to chlorine. [ABSTRACT FROM AUTHOR]