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Improved Synthesis of [Si6Cl14]2-Salts as Precursors for Si6H12and other Novel Silanes

Conference ·
OSTI ID:971608

The reaction of excess HSiCl{sub 3} with the aforementioned triamines led to the formation of [Si{sub 6}Cl{sub 14}]{sup 2-} containing salts in all instances. The isolated complex salts were characterized using FT-IR and elemental analysis. IR spectra of these compounds showed characteristic Si-H stretching modes around 2100cm{sup -1} due to the hexacoordinate silane cation and Si-Cl active modes near 528cm{sup -1} as a result of the cyclic dianion. Reaction yields and elemental analysis (CHN) of the salts are summarized in a table. The reaction of peralkylated triamines with HSiCl{sub 3} in dry CH{sub 2}Cl{sub 2} gives ionic compounds based upon the tetradecachlorocyclohexasilane dianion. Several substituted triamines(R{sub 2}NC{sub 2}H{sub 4}NR{prime}C{sub 2}H{sub 4}NR{sub 2}where R = R{prime} = Et, {sup n}Pr; R = Et, R{prime}= {sup n}Bu, {sup n}Hexyl, Benzyl) were examined for this reaction and N,N,N{prime},N{prime}-tetraethyl-N{sup {double_prime}}-benzyl-diethylenetriamine produced the best yields of [Si{sub 6}Cl{sub 14}]{sup 2-} salt at 23% based on the amine reagent. This improvement in yield could be attributed to the decreased nucleophilicity of the central amine through increased steric hindrance of the alkyl substituents. The overall consequence of this substituent variation study has revealed new reagents for the synthesis of [Si{sub 6}Cl{sub 14}]{sup 2-} salts and further demonstrated the ability of triamines to efficiently dismutate, complex, and condense chlorosilanes. The increased production of these salts has also opened a route for the study of Si{sub 6}X{sub 12} and its Lewis acid/base adducts.

Research Organization:
North Dakota State University
Sponsoring Organization:
USDOE Assistant Secretary for Energy Efficiency and Renewable Energy (EE)
DOE Contract Number:
FG36-08GO88160
OSTI ID:
971608
Report Number(s):
DOE/GO/88160-7
Country of Publication:
United States
Language:
English

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