Discrete Organofluoroaluminate Anions: Synthetic, Structural, and Spectroscopic Aspects

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Abstract

The reaction of alkylaluminum compounds (AlR3, R = Me, n-Bu) with the series of imidazolium-based fluorinating reagents [IPrH][F], [IPrH][(HF)F] and [IPrH][(HF)2F] led to the isolation of salts containing discrete triorganofluoroaluminate ([R3AlF]-), diorganodifluoroaluminate ([R2AlF2]-), and organotrifluoroaluminate ([RAlF3]-) anions, respectively. The formation of [R2AlF2]- and [RAlF3]- anions was accompanied by the release of RH. The syntheses are effective, selective, and straightforward. The related reactions of an arylaluminum compound (AlPh3) resulted in a mixture of different phenylfluoroaluminate anions. All of the obtained products were characterized by NMR and Raman spectroscopy. Structural features of [IPrH][Me2AlF2] (2), [IPrH][MeAlF3] (3), [IPr][AlF4] (4), [IPrH][n-Bu3AlF] (5), [IPrH][n-Bu2AlF2] (6), [IPrH][n-BuAlF3] (7), [IPrH][Ph3AlF] (8), and [IPrH][PhAlF3] (10) were determined by single-crystal X-ray diffraction and compared with DFT calculations of structurally optimized salts.

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Gruden, E., Tramšek, M., & Tavčar, G. (2022). Discrete Organofluoroaluminate Anions: Synthetic, Structural, and Spectroscopic Aspects. Organometallics, 41(1), 41–51. https://doi.org/10.1021/acs.organomet.1c00601

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