Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 30, Pages 9234-9239Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201402655
Keywords
density functional calculations; inverse sandwich complexes; perchlorinated silanes; reaction mechanisms; reactive intermediates
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Funding
- Beilstein-Institut, Frankfurt/Main (Germany)
- Beilstein-Institut
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A surprisingly simple preparative procedure, addition of Si2Cl6 to a solution of [nBu(4)N] Cl in CH2Cl2, leads to the formation of the chloride-complexed cyclic dianions [Si6Cl12 center dot 2Cl](2-), [(SiCl3)Si6Cl11 center dot 2Cl](2-), or [1,y-(SiCl3)(2)Si6Cl10 center dot 2Cl](2-) (y=1, 3, 4), depending on the stoichiometric ratio of the reactants and the reaction temperature (25-85 degrees C). Below -40 degrees C the open-chain oligosilane chloride adducts [Si3Cl9](-), [Si3Cl10](2-), [Si4Cl11](-), and [Si6Cl15](-) are formed, again depending on the reaction conditions chosen. All species were characterized by X-ray crystallography. The underlying reaction mechanism is elucidated by DFT calculations. It incorporates all experimental findings and involves a few key elementary steps: 1) chloride-induced liberation of SiCl3- or higher silanides, 2) their addition to neutral silanes yielding larger oligosilane chloride adducts, 3) dimerization of larger silanides to (substituted) cyclohexasilane dichloride adducts with inverse sandwich structure.
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