Gold Complexes with Potentially Tri- and Tetradentate Phosphinothiolate Ligands.

Reactions of [Au(PPh3)Cl], (Bu4N)[AuCl4] and the organometallic gold complex [Au(damp-C1,N)Cl2] (damp- = 2-(N,N-dimethylamino-methyl)phenyl) with the potentially tri- and tetradentate proligands PhP(C6H3-SH-2-R-3)2 (H2L1a: R = SiMe3, H2L1b: H) and P(C6H3-SH-2)3 (H3L2) result in the formation of mono- or dinuclear gold complexes depending on the precursor used. Monomeric complexes of the type [AuL1Cl] are formed upon the reaction with [Au(damp-C1,N)Cl2], but small amounts of dinuclear [AuL1]2 complexes with gold in two different oxidation states, +I and +III, have been isolated as side-products. The dinuclear compounds are obtained in better yields from [AuCl4]-. A dinuclear complex having two Au(III) centres can be isolated from the reaction of [Au(PPh3)Cl] with H3L2, whereas from the reaction with H2L1b the mononuclear [Au(Ph3P)HL1b] is obtained which contains a three-coordinate gold atom.
Comparatively short gold-gold distances have been found in the dinuclear complexes (2.978(2) A and 3.434(1) Å). They are indicative of weak gold-gold interactions, which is unusual for gold(III).