Theoretical Study on the Assembly and Stabilization of a Silicon-Doped All-Metal Aromatic Unit SiAl3-.

We predict the assembly and stabilization of the silicon-doped all-metal aromatic unit SiAl3-based on the density functional calculations on a series of model compounds D(SiAl3)Mq-as well as the saturated compounds D(SiAl3)Mn((D SiAl3-, Cp-(C5H5-); M Li, Na, K, Be, Mg, Ca) and the more extended sandwich-like species. For all six metals, SiAl3-can be assembled only in “heterodecked sandwich” scheme (e.g., CpM(SiAl3)q-) so as to avoid cluster fusion. Interestingly, among all the designed sandwich species, SiAl3-generally prefers to interact with the partner deck at the side (Al−Al or Al−Si bonds) or corner (Si or Al atoms) site, in contrast to the known decks such as Cp-, P5-, N42-, and Al42-, which take the traditional face−face interaction type. Such interaction types present an interesting growth pattern that might be applicable to the assembly of Si-doped all-metal aromatic SiAl3-units into highly extended sandwich complexes. Our results for the first time showed that the electronic, structural, and aromatic properties of the silicon-doped all-metal aromatic SiAl3-could be well-retained during cluster assembly. [ABSTRACT FROM AUTHOR]