Metal tris-o-dioxolene (o-quinone, o-semiquinone, and catecholate) complexes represent an interesting and vivid model system for the demonstration of a relationship between the structure and magnetic properties when considering a series of objects of the same type. After publishing the reviews [1, 2], the metal tris-o-dioxolene complexes containing the symmetric 3,6-di-tert-butyl-o-benzoquinone derivatives with substituents in positions 4 and 5 are described in a number of works. In addition, some earlier unpublished structures of the complexes of this type are reviewed. The substituents in the lateral chains enhance the steric protection of the metal center and, as a consequence, result in the formation of coordination polyhedra uncharacteristic of the tris(dioxolene) complexes, such as a trigonal prism. In turn, the distortion of the structure affects the magnetic properties of the complexes. Only the complexes with the derivatives of sterically hindered o-quinones, 3,5- and 3,6-di-tert-butyl-o-benzoquinones, are considered in the present review. On the one hand, bulky tert-butyl groups prevent the formation of direct intermolecular contacts and, on the other hand, prevent organic reactions to occur at the benzoquinone cycle.