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Reactions of silicon fluorides with picolinic acid (PicH) and its O-trimethylsilyl derivative afforded neutral hexa- or pentacoordinate complexes F2SiPic2 (5) and PhFSiPic2 (6). According to NMR data, complex 5 with SiO2N2F2 fragment exists as a mixture of two isomers with equivalent 5a and non-equivalent 5b fluorine atoms in a 1.5:1 ratio. Quantum chemical calculations at the B3LYP/6-311G** level confirm the stability of the lowest-energy transstructure of 5a.

The synthesis and structure of bis(pyridine-2-carboxy)difluoro(λ6)- and bis(pyridine-2-carboxy)fluorophenyl(λ5)siliconium