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The ability of two NH 3 ligands to engage in simultaneous chalcogen bonds to a hypervalent YF 4 molecule, with Y = S, Se, Te, Po, is assessed via quantum calculations. The complex can take on one of two different geometries. The cis structure places the two ligands adjacent to one another in a pseudo-octahedral geometry, held there by a pair of σ-hole chalcogen bonds. The bases can also lie nearly opposite one another, in a distorted octahedron containing one π-hole and one strained σ-hole bond. The cis geometry is favored for Y = S, while Te, and Po tend toward the trans structure; they are nearly equally stable for Se. In either case, the binding energy rises rapidly with the size of the Y atom, exceeding 30 kcal mol -1 for PoF 4 .

Chalcogen bonding of two ligands to hypervalent YF4(Y = S, Se, Te, Po)

Chalcogen bonding of two ligands to hypervalent YF₄(Y = S, Se, Te, Po)