Fluoride ion chelation by a bidentate phosphonium/borane Lewis acid.

作者: Todd W. Hudnall , Young-Min Kim , Magnus W. P. Bebbington , Didier Bourissou , François P. Gabbaï

DOI: 10.1021/JA804492Y

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摘要: The phosphonium borane [1-Mes2B-2-MePh2P-(C6H4)]+ ([2]+) has been synthesized as an iodide salt by alkylation of 1-Mes2B-2-Ph2P-(C6H4) with MeI. This novel cationic complexes fluoride to afford the corresponding zwitterionic fluoroborate complex 1-FMes2B-2-MePh2P-(C6H4) (2-F) a binding constant in MeOH exceeding that 1-Mes2B-4-MePh2P-(C6H4) ([1]+) at least 4 orders magnitude. Structural and computational results indicate high fluorophilicity [2]+ arises from both Coulombic cooperative effects which lead formation B−F→P interaction F→P distance 2.666(2) A. These results, are supported NBO AIM analyses, show latent phosphorus-centered Lewis acidity moiety can be exploited enhance via chelation.

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