Phosphanchalkogenide und ihre Metallkomplexe. III. Halogenierungsprodukte der Gold(I)komplexe Ph3PEAuX (E = S oder Se; X = Cl, Br oder I)

Abstract

Abstract The complexes Ph3PEAuI (E = S, Se; 1, 2) were obtained from the reaction of Ph3PEAuCl with KI; they are appreciably less stable than their chloro and bromo analogues. The X-ray structures were determined, whereby 1 proved to be contaminated by a small amount of Ph3PS·I2. Oxidation of 1 and 2 with elemental iodine led to the adducts Ph3PEAuI·0.5I2 (3 and 4), but X-ray investigation of a crystal initially assumed to be 3 proved it to be a 1:1 mixture of 3 with the adduct Ph3PS·1.5I2, while in 4 the iodine molecule was severely disordered, which prevented successful refinement of the structure. Decomposition of 4 by loss of gold led to Ph3PSeI2·1.5I2 4a. Complexes Ph3PEAuX (E = S, Se; X = Br, Cl) were oxidized by elemental bromine (X = Br) or PhICl2 (X = Cl) to Ph3PEAuX 3 (5, 6, 9, 10); none of these X-ray structures could be refined satisfactorily because of diffuse scattering phenomena. Further oxidation led to the ionic compounds [Ph3PEX]+ [AuX 4]– (X = Br, E = S, Se: 7, 8; X = Cl, E = S, 11) or [Ph3PSeCl]+ 0.5[Au4Cl10Se2]2– (12), containing the novel groupings P–E–X. X-ray structures confirmed the nature of all four of these compounds, which display longer P–E bonds than the gold(I) starting materials and short X···X and/or E···X contacts between cations and anions.