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Abstract
The reaction of fac(S)-[RhIII(aet)3] (aet = 2-aminoethanethiolate) with [AuIIICl4]− in water gave an S-bridged pentanuclear complex [AuI 3{RhIII-(aet)3}2]3+(1), accompanied by the spontaneous reduction of AuIII to AuI. The crystal structure of 1(NO3)3·4H2O was determined by X-ray crystallography. In 1 two octahedral fac(S)-[Rh(aet)3] units are linked by three linear AuI atoms to form a trigonal-bipyramid-type RhIII 2AuI 3 pentanuclear structure with an averaged AuI-AuI distance of 3.083(5) Å. The two RhIII 2AuI 3 cations contact with each other through one AuI-AuI interaction with a distance of 3.311(3) Å. The optically active δδ-1 was derived from ΔΔΔΔ-[Zn3(OH){Rh(aet)3}4]5+ by reacting with [AuCl4]− in water.