TY - JOUR
T1 - Simultaneous fluoride binding to ferrocene-based heteronuclear bidentate lewis acids
AU - Boshra, Ramez
AU - Venkatasubbaiah, Kristinen
AU - Doshi, Ami
AU - Lalancette, Roger A.
AU - Kakalis, Lazaros
AU - Jäkle, Frieder
PY - 2007/11/26
Y1 - 2007/11/26
N2 - A series of μ2-fluoro-bridged heteronuclear bidentate Lewis acid complexes [K(18-crown-6)THF]+ [Fc(BMeF)(SnMe2Cl)F] - (1-2F), [K(18-crown-6)THF]+ [Fc(BMeF)(SnMe 2F)F]- (1-3F), [K(18-crown-6)THF]+ [Fc(BMePh)(SnMe2Cl)F]- (2-F), and [K(18-crown-6)THF] + [Fc(BMePh)(SnMe2F)F]- (2-2F) (Fc = 1,2-ferrocenediyl) was prepared. Compounds 2-F and 2-2F were obtained as a mixture of diastereomers, which arise due to the generation of a stereocenter at boron in addition to their inherent planar chirality. All compounds have been studied in the solid state by single-crystal X-ray diffraction analysis and by multinuclear NMR spectroscopy in solution. As a result of bridging-fluoride interactions, tetrahedral boron and distorted trigonal-bipyramidal tin centers are observed. Comparison with the corresponding monofunctional ferrocenylborates further supports the bridging nature of the fluoride anion. Two-dimensional exchange spectroscopy 19F NMR studies provide evidence for facile intermolecular and intramolecular fluorine exchange processes. All complexes display reversible one-electron oxidation events at lower potentials than those of the tricoordinate ferrocenylborane precursors, which is typical of ferrocenylborate complexes.
AB - A series of μ2-fluoro-bridged heteronuclear bidentate Lewis acid complexes [K(18-crown-6)THF]+ [Fc(BMeF)(SnMe2Cl)F] - (1-2F), [K(18-crown-6)THF]+ [Fc(BMeF)(SnMe 2F)F]- (1-3F), [K(18-crown-6)THF]+ [Fc(BMePh)(SnMe2Cl)F]- (2-F), and [K(18-crown-6)THF] + [Fc(BMePh)(SnMe2F)F]- (2-2F) (Fc = 1,2-ferrocenediyl) was prepared. Compounds 2-F and 2-2F were obtained as a mixture of diastereomers, which arise due to the generation of a stereocenter at boron in addition to their inherent planar chirality. All compounds have been studied in the solid state by single-crystal X-ray diffraction analysis and by multinuclear NMR spectroscopy in solution. As a result of bridging-fluoride interactions, tetrahedral boron and distorted trigonal-bipyramidal tin centers are observed. Comparison with the corresponding monofunctional ferrocenylborates further supports the bridging nature of the fluoride anion. Two-dimensional exchange spectroscopy 19F NMR studies provide evidence for facile intermolecular and intramolecular fluorine exchange processes. All complexes display reversible one-electron oxidation events at lower potentials than those of the tricoordinate ferrocenylborane precursors, which is typical of ferrocenylborate complexes.
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U2 - 10.1021/ic7013754
DO - 10.1021/ic7013754
M3 - Article
C2 - 17979272
AN - SCOPUS:37249006266
SN - 0020-1669
VL - 46
SP - 10174
EP - 10186
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 24
ER -