5 years ago

The Tris(pentafluoroethyl)stannate(II) Anion, [Sn(C2F5)3]−—Synthesis and Reactivity

The Tris(pentafluoroethyl)stannate(II) Anion, [Sn(C2F5)3]−—Synthesis and Reactivity
Mark Niemann, Beate Neumann, Markus Wiesemann, Berthold Hoge, Johannes Klösener, Hans-Georg Stammler
Syntheses of salts containing the tris(pentafluoroethyl)stannate(II) ion, [Sn(C2F5)3]−, were achieved through deprotonation of the corresponding stannane, HSn(C2F5)3, as well as by direct pentafluoroethylation of SnCl2 with LiC2F5. The electron-withdrawing substituents have substantial influence on the stability and reactivity of the anion as documented by its treatment with main group halides. Alkyl halides (R−X) underwent nucleophilic substitutions to afford RSn(C2F5)3, whereas Si, Ge, Sn, P halides gave rise to oxidation processes yielding hypervalent [SnX2(C2F5)3]− salts (X=Cl, Br, I). Moreover the unsymmetrical distannane, nBu3SnSn(C2F5)3, was disclosed as an alternative precursor for the Sn(C2F5)3 moiety. Although neither the solid state structure nor its spectra in alkane solution reveal unexpected peculiarities, unusual dissociation of the compound in coordinating solvents into [nBu3Sn(D)n]+ and [Sn(C2F5)3]− ions was observed. An acidic stannane: Introduction of three electron-withdrawing pentafluoroethyl groups results in a stannane, HSn(C2F5)3, which is fully deprotonated in water. The corresponding base [Sn(C2F5)3]− exhibits remarkable stability. In this contribution we present various protocols for [Sn(C2F5)3]− salt formation and present the reactivity towards carbon and element halides as well as transition-metal complexes.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702855

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