Fluoride ion chelation by a bidentate phosphonium/borane lewis acid

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

Research output: Contribution to journalArticle

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Abstract

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

Original languageEnglish
Pages (from-to)10890-10891
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number33
DOIs
StatePublished - 20 Aug 2008

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Boranes
Lewis Acids
Alkylation
Chelation
Fluorides
Acidity
Phosphorus
Ions
Salts
Acids
Iodides

Cite this

Hudnall, Todd W. ; Kim, Young Min ; Bebbington, Magnus ; Bourissou, Didier ; Gabbaï, François P. / Fluoride ion chelation by a bidentate phosphonium/borane lewis acid. In: Journal of the American Chemical Society. 2008 ; Vol. 130, No. 33. pp. 10890-10891.
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abstract = "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 borane complexes fluoride to afford the corresponding zwitterionic fluoroborate complex 1-FMes2B-2-MePh2P-(C6H4) (2-F) with a binding constant in MeOH exceeding that of 1-Mes2B-4-MePh2P-(C6H4) ([1]+) by at least 4 orders of magnitude. Structural and computational results indicate that the high fluorophilicity of [2]+ arises from both Coulombic and cooperative effects which lead to formation of a B-F→P interaction with a F→P distance of 2.666(2) {\AA}. These results, which are supported by NBO and AIM analyses, show that the latent phosphorus-centered Lewis acidity of the phosphonium moiety in [2]+ can be exploited to enhance fluoride binding via chelation.",
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Fluoride ion chelation by a bidentate phosphonium/borane lewis acid. / Hudnall, Todd W.; Kim, Young Min; Bebbington, Magnus; Bourissou, Didier; Gabbaï, François P.

In: Journal of the American Chemical Society, Vol. 130, No. 33, 20.08.2008, p. 10890-10891.

Research output: Contribution to journalArticle

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AU - Kim, Young Min

AU - Bebbington, Magnus

AU - Bourissou, Didier

AU - Gabbaï, François P.

PY - 2008/8/20

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