Synthesis and Structure of Gold Complexes [Ph3PR][Au(CN)2Cl2] (R = CH2CH=CHCH3, CH2CN) and Ph3PC(H)(CN)Au(CN)2Cl

The ionic complexes [Ph 3 PR][Au(CN) 2 Cl 2 ] (R = CH 2 CH=CHCH 3 ( I ), CH 2 CN ( 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 Ph 3 PC(H)(CN)Au(CN) 2 Cl ( 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) 2 Cl 2 ] − , 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.