Trialkylsilyl-Substituted Silole and Germole Dianions as Precursors for Unusual Silicon and Germanium Compounds.

Group 14 element heteroles are the heavier analogues of cyclopentadienes in which a heavier group 14 element atom replaces the sp carbon atom. In particular siloles and, to a somewhat smaller degree, germoles attracted considerable attention since the early 1990s due to their favorable photophysical properties which allowed the construction of OLEDs using group 14 element heteroles as emissive or electron-transport layers. Anions and in particular dianions derived from group 14 element heteroles have been of substantial interest due to the possible occurrence of Hückel aromaticity involving the heavier main group atom. Aromaticity is not the only notable electronic feature of silole and germole dianions; the spatial and energetic alignment of their frontier orbitals is equally remarkable. With a high lying lone pair at the heteroatom, which is orthogonal to a delocalized π-system, their frontier orbital sequence closely resembles that of N-heterocyclic carbene analogues. Despite these intriguing parallels between carbene analogues and silole and germole dianions, disappointingly little is known about their reactivity. The installation of trialkylsilyl substituents in the 2,5-positions of the heterocyclopentadiene ring as in K[] has a remarkable effect on the stability of silole and germole dianions and allows us to study their reactivity and to evaluate their synthetic potential in detail. Simple double salt metathesis reactions with different dihalides provided heterofulvenes. These were detected either as intermediates or, in the case of carbon dihalides, isolated in the form of their ylidic isomers . In other cases, the heterofulvenes were the starting point for complex reaction sequences leading to novel binuclear complexes of titanium and zirconium or for simple isomerization reactions that lead to bicyclohexene-type tetrylenes (BCH-tetrylenes) , a novel class of heavier carbenes. These bicyclic carbene analogues are significantly stabilized by homoconjugation between the electron deficient tetrel atom and the remote C═C double bond. Compound with E'R═SiR and E = Si is a valence isomer of disilabenzene and is a stable derivative of the global minimum of the SiCH potential energy surface. With group 13 dihalides, as for example with boron dichlorides, topological closely related compounds were isolated. These Ge(II) complexes of borole dianions are isolobal to half-sandwich complexes of main group elements such as aluminum(I) cyclopentadienide or can be viewed as nido-type clusters. These analogies already open a broad field for future investigations of their reactivity. Trialkylsilyl-substituted heterole dianions provide a facile synthetic approach to several novel intriguing compound classes with the tetrel element in unusual coordination states. The reactivity and the synthetic potential of these new compounds is however widely unexplored and calls for future systematic studies. Gratifyingly, the periodic table of the elements stills holds a lot of potential for future research on the reactivity of silole and germole dianions.