Abstract
A detailed analysis of monodentate and bidentate complexation of tris(pentafluorophenyl)silyl (TPFS) derivatives with neutral Lewis bases was performed. The NMR spectroscopy and X-ray diffraction analysis (11 structures) were the key methods to characterize tetra- or pentacoordinate silicon compounds, whereas the peculiarities of crystal packing were analyzed by means of DFT calculations. The interaction of TPFS-X (X = F, Cl, OTf) with strong Lewis bases (HMPA, N-methylpyrrolidinone) may afford three different species: neutral pentacoordinate TPFS(X)-L, cationic tetracoordinate TPFS-L + X −, and cationic pentacoordinate TPFS-(L) + 2X −, representatives of each type were characterized by X-ray diffraction. A variety of complexes with bidentate complexation, featuring the trigonal bipyramidal geometry with apical C 6F 5-group was prepared and structurally characterized. The extent of Si–C apical bond elongation depends on the donating ability of the coordinating ligand, with the longest Si–C bond of 1.981(1) Å observed for six-membered complex of TPFS-ether of N-(2-hydroxybenzoyl)pyrrolidine.
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