Reactions of R-NiF{sub 3} and K{sub 2}NiF{sub 6} with N(CH{sub 3}){sub 4}{sup +} in HF: Synthesis of N(CF{sub 3}){sub 3} and the novel N(CHF{sub 2}){sub 4}{sup +} cation
- Lawrence Berkeley National Lab., CA (United States)
K{sub 2}NiF{sub 6} in solution in anhydrous HF (aHF) and R-NiF{sub 3}, suspended in aHF, are shown to be excellent fluorinators of N(CH{sub 3}){sub 4}{sup +} below room temperature. Reaction with R-NiF{sub 3} (-60 to 0 {degrees}C) results in quantitative yields of N(CF{sub 3}){sub 3}, and CF{sub 4}. This is akin to the Simons electrochemical fluorination at a nickel anode, which has long been speculated to involve the formation of a higher fluoride of nickel, NiF{sub x}(x>2), at the anode surface. Dropwise addition of an aHF solution of K{sub 2}NiF{sub 6} to a solution of N(CH{sub 3}){sub 4}{sup +} AsF{sub 6}{sup -} in aHF held at -70{degrees}C resulted in a mixture of N(CHF{sub 2}){sub 4}{sup +} (74.4%) and N(CH{sub 3}){sub 4}{sup +} (25.6%), with no C-N bond cleavage products (i.e., CF{sub 4} or CHF{sub 3}). Reaction of N(CH{sub 3}){sub 4}{sup +} AsF{sub 6}{sup -} with an excess of K{sub 2}NiF{sub 6} at -70{degrees}C in aHF resulted in a mixture of N(CHF{sub 2}){sub 4}{sup +} (27.8%), N(CF{sub 3}){sub 3} (38.9%) and CF{sub 4} (33.3%). This indicates that further fluorination of N(CHF{sub 2}){sub 4}{sup +} results in C-N bond cleavage to give N(CF{sub 3}){sub 3} and CF{sub 4}; more highly fluorinated cations such as N(CF{sub 3}){sub 4}{sup +}, are not observed. The N(CHF{sub 2}){sub 4}{sup +} cation, reported for the first time, has been characterized in aHF by {sup 1}H, {sup 19}F, {sup 13}C and {sup 14}N NMR spectroscopy.
- OSTI ID:
- 560026
- Report Number(s):
- CONF-970443-; TRN: 97:005895-0105
- Resource Relation:
- Conference: 213. national meeting of the American Chemical Society, San Francisco, CA (United States), 13-17 Apr 1997; Other Information: PBD: 1997; Related Information: Is Part Of 213th ACS national meeting; PB: 2904 p.
- Country of Publication:
- United States
- Language:
- English
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