"Inverse Sandwich" Complexes of Perhalogenated Cyclohexasilane
Perhalogenated cyclohexasilanes, Si6X12 (X = Cl, Br), were prepared by reaction of Si6H12 with molecular chlorine or bromine in cold (-89 °C) dichloromethane. Single-crystal structural determination by X-ray analysis shows that the six silicon atoms comprising Si6Br12 adopt a chair conformation in the solid state. The addition of p-tolunitrile to Si6X12 (X = Cl, Br) leads to the rapid formation of colorless precipitates. Si6Br12 3 2(p-CH3C6H4CN) adopts an 'inverse sandwich' structure where the N atoms of the p-tolunitrile molecules are μ6 bonded and are located above and below the planar hexagonal Si6 ring. In conclusion, Si6X12 (X = Cl, Br) was synthesized by molecular halogenation of Si6H12 in high yield and good purity. Perhalogenated cyclohexasilanes react with p-tolunitrile to give 'inverse sandwich' adducts 3 and 4 with a planar Si6 ring upon coordination. Our future reports will detail dianionic adducts based on tetra-n-butylammonium halides as well as a monoanionic adamantyl azide adduct of Si6Cl12. It is straightforward to conceptualize the utility of Si6X12 ∙ Ln chemistry in molecular assembly of silicon-based clusters/tubes/wires. Thereby, we proffer that this constitutes a new landscape in Si chemistry.
- Research Organization:
- North Dakota State Univ., Fargo, ND (United States)
- Sponsoring Organization:
- USDOE Assistant Secretary for Energy Efficiency and Renewable Energy (EE)
- DOE Contract Number:
- FG36-08GO88160
- OSTI ID:
- 977243
- Report Number(s):
- DOE/GO/88160-13; ORGND7; TRN: US201206%%143
- Journal Information:
- Organometallics, Vol. 29, Issue 10; ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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