Epsilon Open Archive

Abstract

The coordination chemistry of d(10)s(2) metal ions is strongly affected by an (at least partially) occupied d(10)s(2) metal ion-ligand atom antibonding orbital, which may cause a void in the coordination sphere due to repulsion between the electrons in the antibonding orbital on the metal ion and those on the ligands. The character of the formed d(10)s(2) metal ion-ligand atom bond plays an important role in the electron density in the antibonding orbital and thereby also in the coordination chemistry. The hydrated tin(II) ion, [Sn(H2O)(3)](2+), and the trihydroxidostannate ion, [Sn(OH)(3)](-), have very different mean Sn-O bond lengths (2.21 and 2.08 angstrom, respectively) and O-Sn-O angles (ca. 78 and 90 degrees, respectively) both in the solid state and in solution. On increasing the covalency of the tin(II)-ligand bonds, the repulsion decreases and higher coordination numbers are obtained, as seen in the dimethylsulfoxide- and N,N-dimethylthioformamide-solvated tin(II) ions, both of which are five-coordinate with square-pyramidal structures.