The structure of trimethyltin fluoride

Abstract

The solid-state structure of (CH3)3SnF was reinvestigated by X-ray diffraction techniques as well as by multi-nuclear solid-state NMR spectroscopy. Trimethyltin fluoride crystallizes from hot ethanol in the orthorhombic space group Pnma at room temperature and changes to a low-temperature orthorhombic phase (space group: Cmcm) below -70 °C. In both modifications, trimethyltin fluoride adopts a linear chain structure with symmetric fluorine bridges, in contrast to previous reports. During its synthesis, (CH3)3SnF precipitates in another, poorly crystalline modification, as shown by powder X-ray diffraction. Solid-state MAS NMR experiments of both room-temperature phases of (CH3)3SnF (non-recrystallized and recrystallized) were carried out for the (1)H, (13)C, (19)F, and (119)Sn nuclei. The (119)Sn{(19)F, (1)H} and (19)F{(1)H} NMR spectra offer unambiguous determination for the (19)F and (119)Sn shielding tensors. The (119)Sn{(1)H} solid-state NMR spectra are in agreement with pentacoordination of Sn in this compound for the non-recrystallized and the recrystallized modifications. Based on the solid-state NMR results, the non-recrystallized modification of (CH3)3SnF also consists of linear, symmetrically fluorine-bridged chains, and differs from the recrystallized orthorhombic phase only in packing of the chains.

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

“…23, top) (the Nc value for Sn···F is 0.91; the F-Sn···F angle is 178.85°). Similar behavior is shown by several other organotin derivatives bearing one, two, or three halogen atoms at the heavy tetrel [113][114][115][116] (Fig. 23).…”

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

“…Chloride/fluoride exchange reactions using Me 3 SnF Me 3 SnF is a useful fluorinating agent, its polymeric structure makes it insoluble in most solvents, 40,41 but it dissolves as the Cl/F exchange reaction proceeds, and usually, the Me 3 SnCl (which contains tbp tin centres weakly chlorine-bridged into polymeric chains) 42 formed is easily removed from the products by washing with hexane. The reagent does not provide free fluoride ions so an excess can be used without the risk of the decomposition observed using [NMe 4 ]F. The fac-octahedral trifluoro complexes [ScF 3 (R 3 -tacn)] were readily obtained by treatment of the trichloro species with three mol.…”

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

“…The resulting Me 3 SnX (X = Cl, Br, I) byproduct is easily removed under reduced pressure, and the uranium(V) fluoride ( 4 ) is obtained in excellent yields (79–98 %) following work up. If desired, the Me 3 SnX (X = Cl, Br, I) can be subsequently converted back into Me 3 SnF by reaction with aqueous KF solution , , . When the reactions are monitored by 1 H NMR spectroscopy in [D 6 ]benzene, resonances corresponding to the uranium(V) imido halide complex ( 4 ), in addition to singlets at δ = 0.29, 0.40, and 0.48, are observed for Me 3 SnX (X = Cl, Br, and I), respectively, consistent with a halide exchange reaction .…”

“…Roesky and co‐workers pioneered the use of Me 3 SnF as a reagent for the metathesis of chlorides to the corresponding fluorides . Although this compound forms a polymeric chain‐like structure of tin and fluorine atoms in the solid state, it has been shown to react with metal chlorides to generate metal fluorides and volatile trimethyltin chloride. [23b], [23c], Specifically, Me 3 SnF has been used to prepare a variety of alkaline‐earth (Mg, Ca, Sr), early (Sc, Y, Ti,[23a], , Zr,[23a], [30h], Hf,[23a], [31b], [31c], [31d], [31e] V, Nb, Ta), mid (W[30j], ), and late (Fe, Co, Zn) transition‐metal, main‐group (Al, Ga,[39g] Si,[23c], Ge, Sb, P[23b], ) and lanthanide‐metal (Sm, Ho, Er) organometallic and inorganic fluoride complexes.…”