The metallathiacrown ethers cis-Mo(CO) 4 {2,2′-(C 12 H 8 O 2 )PO-(CH 2 CH 2 S) n CH 2 CH 2 OP(2,2′-(O 2 H 8 C 12 ))} (n = 2, 3) and cis-Mo(CO) 4 {2,2′-(C 12 H 8 O 2 )POCH 2 CH 2 S-1-(C 6 H 4 )-2-SCH 2 CH 2 OP(2,2′-(O 2 H 8 C 12 ))} have been prepared as soft metal selective molecular receptors. Multinuclear NMR spectroscopy and X-ray crystallography have been used to show that byproducts formed during the syntheses of the metallathiacrown ethers cis-Mo(CO) 4 {2,2′-(C 12 H 8 O 2 )PO(CH 2 CH 2 S) n CH 2 CH 2 OP(2,2′-(O 2 H 8 C 12))} (n = 2, 3) are homobinuclear complexes with cis-Mo(CO) 4 (P-donor)(S-donor) centers. The abilities of the metallathiacrown ethers to bind PdCl 2 and PtCl 2 have been assessed using 31 P{ 1 H} NMR spectroscopy and X-ray crystallography. The complexes showed null results with PdCl 2 ; however, the PtCl 2 experiments showed that the complexes cis-Mo(CO)}]PtCl 2 } (n = 2, 3) complexes. The 31 P{ 1 H} NMR spectra of these complexes suggest a cis-PtS 2 Cl 2 coordination environment in each, which leads to asymmetric binding in the latter complex. Binding of HgCl 2 by the complexes cis-Mo(CO) 4 {2,2′-(C 12 H 8 O 2 )PO(CH 2 CH 2 S) n CH 2 CH 2 OP(2,2′-(O 2 H 8 C 12 ))} (n = 2, 3) has been studied using 31 P{ 1 H} NMR spectroscopy. Each complex was titrated with HgCl 2 , and the quantitative shifts in the 31 P{ 1 H} NMR spectra were fit to a binding mechanism. The n = 2 metallathiacrown ether binds HgCl 2 to form a 1:1 complex with K a = 12.0(0.2) M −1 . In contrast, interaction of HgCl 2 with the n = 3 metallathiacrown ether results in isomerization to the trans complex, and HgCl 2 binds to both isomers. A model has been adapted to fit the titration data of this complex and to extract equilibrium constants for each step in the cycle: the cis−trans equilibrium of the free, K free (0.570 (0.004)), and bound, K bound (0.16 (0.03)), metallathiacrown ethers, as well as the association binding constants for the cis, K cis ([4.1(0.3)] × 10 2 M −1 ) and trans, K trans ([1.1(0.2)] × 10 2 M −1 ), metallathiacrown ethers. The equilibrium constants demonstrate that the cis metallathiacrown ether binds more strongly to the HgCl 2 than does the trans metallathiacrown ether and that the cis−trans equilibrium favors the cis metallathiacrown ether.