Siliconoid Expansion by a Single Germanium Atom through Isolated Intermediates.

The growth of (semi-)metal clusters is pivotal for nucleation processes in gaseous and condensed phases. We now report the isolation of intermediates during the expansion of a stable unsaturated silicon cluster (siliconoid) by a single germanium atom through a sequence of substitution, rearrangement and reduction. The reaction of ligato-lithiated hexasilabenzpolarene LiSi Tip (1Li⋅(thf) , Tip=2,4,6-triisopropylphenyl) with GeCl ⋅NHC (NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) initially yields the product with exohedral germanium(II) functionality, which then inserts into an Si-Si bond of the Si scaffold.

Exohedral functionalization core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization.

Taking advantage of pendant tetrylene side-arms, stable unsaturated Si silicon clusters (siliconoids) with the benzpolarene motif (the energetic counterpart of benzene in silicon chemistry) are successfully employed as ligands towards Group 9 metals. The pronounced σ-donating properties of the tetrylene moieties allow for sequential oxidative addition and reductive elimination events without complete dissociation of the ligand at any stage. In this manner, either covalently linked or core-expanded metallasiliconoids are obtained.

Nickel-assisted complete cleavage of CO by a silylene/siliconoid hybrid under formation of an Si[double bond, length as m-dash]C enol ether bridge.

Reaction of a silylene-functionalized Si6 siliconoid with CO in the presence of catalytic quantities of a nickel(0) complex results in the complete cleavage of the CO triple bond, but preserves the Si6 scaffold with an exohedrally incorporated Si[double bond, length as m-dash]C enol ether bridge. The uncompromised cluster core emphasizes the role of the so-called benzpolarene motif as the energetic silicon pendants of benzene in carbon chemistry.

Chalcogen-Expanded Unsaturated Silicon Clusters: Thia-, Selena-, and Tellurasiliconoids.

Reactions of silylenes with heavier chalcogens (E) typically result in Si=E double bonds or their π-addition products. In contrast, the oxidation of a silylene-functionalized unsaturated silicon cluster (siliconoid) with Group 16 elements selectively yields cluster expanded siliconoids Si E (E=S, Se, Te) fully preserving the unsaturated nature of the cluster scaffold as evident from the NMR signatures of the products. Mechanistic considerations by DFT calculations suggest the intermediacy of a Si siliconoid with exohedral Si=E functionality.

Indirect and Direct Grafting of Transition Metals to Siliconoids.

Unsaturated charge-neutral silicon clusters (siliconoids) are important as gas-phase intermediates between molecules and the elemental bulk. With stable zirconocene- and hafnocene-substituted derivatives, we here report the first examples containing directly bonded transition-metal fragments that are readily accessible from the ligato-lithiated Si siliconoid (1Li) and Cp MCl (M=Zr, Hf). Charge-neutral siliconoid ligands with pending tetrylene functionality were prepared by the reaction of amidinato chloro tetrylenes [PhC(NtBu) ]ECl (E=Si, Ge, Sn) with 1Li, thus confirming the principal compatibility of such low-valent functionalities with the unsaturated Si cluster scaffold.

Site-selective functionalization of SiR siliconoids.

The recent progress in the synthesis of partially substituted neutral silicon clusters (siliconoids) revealed unique structures and electronic anisotropies that are reminiscent of bulk and nano surfaces of silicon. Here, we report the selective 2-lithiation of the global minimum SiR siliconoid at a different vertex than in the previously reported isomeric 4-lithiated derivative (R = 2,4,6- PrCH). In order to enable an intuitive distinction of the vertices of the global minimum SiR scaffold (which can be considered the silicon analogue of benzene in terms of thermodynamic stability), we introduce a novel nomenclature in analogy to the -- nomenclature of disubstituted benzenes.