The divalent metal complexes M-II{(SC6H4-2-PR2)-kappa S-2,P}(2) (3-7, and 9-11) (M= Zn, Sn, or Pb; R = Pr-i, Bu-t, or. Ph); the Sn(W) complexes :Sn{(SC6H4-2-PR2)-kappa(2)-S,P}Ph2Cl (12 and 13) (R = Pr-i and Bu-t), and the ionic Sn(IV) complexes [Sn{(SC6H4-2-PR2)-kappa(2)-S,P}Ph-2[BPh4] (14 and 15) (R = Pr-i and Bu-t) have been prepared and characterized by multinuclear NMR spectroscopy and single. crystal X.-ray diffraction when suitable crystals were afforded The Sn(II) and Pb(II) complexes with R = Ph, Pr-i, or Bu-t (5, 6, 9, and 10) demonstrated ligand "folding" hinging on the P,S vector-a behavior driven by the repulsions of the metal/phosphorus and:metal/sulfur lone Pairs and increased M-S sigma bonding strength. This phenomenon Was examined by density functional theory (DFT) calculations for the compounds in both folded and unfolded states. The Sn(IV) compound 13 (R = Bu-t) crystallized with the phosphine in an axial position of the pseudotrigonal bipyramidal complex and also exhibited hemilability in the Sn P dative bond, while compound 12 (R = Pr-i), interestingly, crystallized with phosphine in an equatorial position and did not show hemilability. Finally, the crystal structure of 15 (R = Bu-t) revealed the presence of an uncommon, 4-coordinate, stable Sn(IV) cation.