Synthesis and Structure of the Ionic Complexes [Ph3PEt][Au(CN)2Cl2] and [Ph3PCH2CH2Br][Au(CN)2Br2]

• Published in: Russian journal of coordination chemistry Vol. 49; no. 3; pp. 184 - 188
• Main Authors: Shevchenko, D. P., Khabina, A. E.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01.03.2023; Springer Nature B.V
• Subjects: Angles (geometry); Anions; Cations; Chemistry; Chemistry and Materials Science; Crystallography; Halides; Hydrogen bonds; Inorganic Chemistry; Physical Chemistry; X-ray diffraction; synthesis; X‑ray diffraction analysis; potassium dihalodicyanoaurates; structure; organyltriphenylphosphonium halides
• ISSN: 1070-3284; 1608-3318
• DOI: 10.1134/S1070328423700392

The reactions of potassium dichloro- and dibromodicyanoaurate with appropriate ethyl and (2‑bromoethyl)triphenylphosphonium halides in water gave new dihalodicyanoaurate complexes [Ph 3 PE-t][Au(CN) 2 Cl 2 ] ( I ) and [Ph 3 PCH 2 CH 2 Br][Au(CN) 2 Br 2 ] ( 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) 2 Cl 2 ] – in I have a nearly undistorted square planar geometry, whereas the geometry of the [Au(CN) 2 Br 2 ] – 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.