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Transition-Metal Complexes Featuring Dianionic Heavy Group 14 Element Aromatic Ligands.

The synthesis of dilithio-stannoles and -plumboles, dianionic aromatic compounds containing tin and lead atoms in their π-skeletons, opened a new field of transition-metal chemistry. Since the discovery of ferrocene (Cp2Fe), which is composed of anionic aromatic ligands (Cp: cyclopentadienyl) and Fe(II), ferrocene-type sandwich complexes have long played important roles in many fields of chemistry. During the last few decades, the electronic and structural properties of the Cp ligand have been modified by introducing electron-donating, electron-withdrawing, and sterically encumbered substituents on the skeletal carbon atoms to obtain desirable properties of the resulting sandwich complexes. In terms of modifying the Cp ligand, we focused our attention on introducing a heavy group 14 atom into the π-skeleton. This idea was originally inspired by a question of whether or not aromaticity was retained after the replacement of a skeletal carbon atom by a heavy group 14 atom. After we succeeded in the synthesis of aromatic dilithio-stannoles and -plumboles, revealing that the concept of conventional aromaticity was expanded to lead-containing π-systems, we undertook the present project on applying these dianionic aromatic heavy Cp analogues as ligands for transition-metal complexes. The combination of a stannole and Cp*Ru units accomplished the creation of a neutral triple-decker complex and an anionic ruthenocene, which was not be accessible using Cp and its related ligands that are composed of only carbon atoms. The anionic ruthenocene reacted with electrophiles to afford ruthenocene-type sandwich complexes, and the structures of the stannole skeletons were highly dependent on the substituents on the tin atoms, in sharp contrast to the planar Cp ligand. The dianionic plumbole ligand was also found to function as an η5-coordinating ligand in an anionic ruthenocene, which is noteworthy in terms of incorporating the heaviest group 14 atom into a π-ligand to produce a ferrocene-type sandwich complex. The anionic ruthenocene bearing the plumbole ligand reacted with electrophiles to afford ruthenocene-type plumbole complexes, which have oxidation potentials lower than those of the corresponding tin analogues, demonstrating the effect of introduction of a lead atom heavier than a tin atom. In the reactions of dilithiostannoles with group 4 metals, the resulting complexes were found to have exotic electronic structures that cannot be constructed by the Cp ligand. The transition-metal complexes derived from dilithio-stannoles and -plumbole therefore exhibit remarkable differences as well as similarities to the traditional Cp-based transition-metal complexes. These results spotlight the introduction of heavy group 14 atoms into carbon-based π-skeletons, which can perturb the electronic properties of conventional transition-metal complexes and open a new chemistry of transition-metal complexes.