The reactions of fac-[Rh(apt)3] (apt: 3-aminopropanethiolate) with PdII and ZnII gave S-bridged RhIII2ZnII trinuclear and RhIII3PdII3 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. The reactions of fac-[Rh(3-aminopropanethiolato-N,S)3] having six-membered chelate rings with PdII and ZnII gave S-bridged RhIII2ZnII trinuclear and RhIII3PdII3 hexanuclear complexes, respectively, the structures of which are entirely different from those derived from fac-[Rh(2-aminoethanethiolato-N,S)3] having five-membered chelate rings.

Treatment of fac-[Rh(apt)₃] (apt = 3-aminopropanethiolate) with [Cu(CH₃CN)₄]⁺ in a 2:3 ratio in water gave a Cu^I₃Rh^III₂ pentanuclear complex ([1_apt]³⁺), in which two octahedral fac-[Rh(apt)₃] units are linked by three linear Cu^I ions through sulfur bridges. Complex [1_apt]³⁺ was oxidized to produce a Cu^ICu^IIRh^III₂ tetranuclear complex, in which two fac-[Rh(apt)₃] units are linked by linear Cu^I and square-planar Cu^II ions. The structure and property of [1_apt]³⁺ were compared with those of the corresponding Cu^I₃Rh^III₂ complex with 2-aminoethanethiolate.

Three dinuclear palladium(II) complexes with 2,2′-bipyridine (bpy) were synthesized from [Pd(bpy)Cl₂] and 3-aminopropanethiol (Hapt) by changing reaction conditions. It was found that Hapt can adopt three different coordination modes (Hapt-κ²S, apt-κN,κ²S, H₋₁apt-κ²N,κ²S) dependent on its protonation states in this coordination system.