Density functional study of structural properties and binding energies of dimethylsulfoxide Ru(II) complexes

Abstract

The structures of a series of Ru(II)–dimethylsulfoxide complexes were optimized using a density functional method. The obtained bond lengths reproduce the experimental trends quite well, although a general overestimate is found. The theory is also used to predict the kind of coordination linkage (via O or S) preferred by dmso when different ancillary ligands are present. The results are consistent with the experimental findings and can be explained in terms of σ–π contributions in the sulfoxide–metal bond. Insight into the strength of the oxygen/sulfur metal bonds is further given by the calculation of the binding energies of the sulfoxide fragments in different situations. Model molecules with emphasized electronic effects are also considered to confirm the trends and to study special aspects such as preferred conformation structures. The general good performance, combined to computational economy, makes the present method suitable for further applications in this field.