Synthesis and structures of tris(pentafluorophenyl)silylamines

Abstract

Tris(pentafluorophenyl)silylamines were synthesized by silylation of amines and imines with (C 6 F 5 ) 3 SiCl or (C 6 F 5 ) 3 SiOTf in the presence of triethylamine. The crystal structures of the (C 6 F 5 ) 3 SiN(H)CH 2 Ph and (C 6 F 5 ) 3 SiN(CH=CMe 2 )CH 2 Ph compounds were studied by X ray diffraction. The crystal packings were analyzed by quantum chemical calculations in terms of the density functional theory (PBE exchange correlation functional).

How do electron donating substituents affect the electronic structure, molecular topology, vibrational properties and intra- and intermolecular interactions of polyhalogenated pyridines?

“…44 Another case reported in the Literature regarded the crystal of tosylate derivatives, wherein a FÁ Á ÁF type contact was discovered with an interaction energy as high as 13 kJ mol À1 ; the analysis of valence electron density indicated to be based on a ''peak-hole'' type of interaction. 45 From a geometrical point of view (Table 4), among the HB dimers, the ones with hydroxyl substituents indicate shorter interatomic distance OHÁ Á ÁN (py) than NH-HÁ Á ÁN (py) for the HB dimers with amino substituents. The HB dimers are co-planar except for the HB dimer for compound 7, wherein two PyX rings are nearly perpendicular to one another (d (O, H, N 6 , C 1 ) = 98.11).…”

Molecular Structures Polymorphism the Role of F…F Interactions in Crystal Packing of Fluorinated Tosylates

“…. F contacts clearly demonstrated that a lone pair of fluorine atoms is directed toward the local depletion of electron density between electron pairs of another fluorine atom [38] ("peak-hole interaction"). QTAIM and ∆ρ maps are very comprehensive tools for unexperienced reader, however, these methods cannot be used to analyze the entire region related to F .…”

Complexation of tris(pentafluorophenyl)silanes with neutral Lewis bases

“…Topological analysis of q(r) have shown that critical points (CP) (3, À1) are found for all chemical bonds including coordination Si-O ones, as well as for weak intermolecular HÁ Á ÁF, OÁ Á ÁH and FÁ Á ÁF interactions. The characteristics of HÁ Á ÁF and FÁ Á ÁF intermolecular interactions in crystals of TPFS derivatives (C 6 F 5 ) 3 SiNR 2 were studied in terms of AIM theory and published previously [25]. The bonds formed by Si and P atoms are characterized by positive values of Laplacian of electron density ($ 2 q(r)) and negative ones of local energy density (E e (r)) in CP(3, À1) that corresponds to intermediate type of interatomic interactions in terms of AIM theory [22].…”