3-Aminopropanethiol versus 2-Aminoethanethiol Leading to Different S-bridged Multinuclear Structures Composed of Rhodium(III) Octahedrons

The reactions of fac-[Rh(apt)(3)] (apt: 3-aminopropanethiolate) with Pd-II and Zn-II gave S-bridged (Rh2ZnII)-Zn-III trinuclear and (Rh3Pd3II)-Pd-III hexanuclear complexes, respectively. The structures of these complexes, determined by single-crystal X-ray crystallography, were quite different from S-bridged structures derived from fac-[Rh(aet)(3)] (aet: 2-aminoethanethiolate). This is ascribed to the difference in S-Rh-S bite angles between fac-[Rh(apt)(3)] with six-membered N, S-chelate rings and fac[Rh(aet)(3)] with five-membered N, S-chelate rings.