For (pentafluoroethyl)phenylstannanes, (C F ) SnPh (n=1-3), and dimethylbis(pentafluoroethyl)stannane, (C F ) SnMe , a high yield synthesis was developed by the use of LiC F as a C F transfer reagent. The treatment of these products with gaseous hydrogen chloride or hydrogen bromide afforded (C F ) SnX (X=Cl, Br; n=1-3) in good yields. The (pentafluoroethyl)stannanes were fully characterized by H, C, F and Sn NMR, IR spectroscopy and mass spectrometry. The treatment of the (pentafluoroethyl)tin halides (C F ) SnX with 1,10-phenanthroline (phen) led to the formation of the corresponding octahedrally coordinated complexes [(C F ) SnX (phen)], the structures of which were elucidated by X-ray diffraction analyses. The bromostannane (C F ) SnBr reacted with sodium cyclopentadienide to give the (η -cyclopentadienyl)tris(pentafluoroethyl)stannane, (C F ) SnCp, for which single-crystal X-ray diffraction analysis could be performed. The coupling constants J( Sn, C) and J( Sn, F) of all new stannanes are strongly correlated and sensitive to the substitution pattern at the tin atom. For both coupling constants a negative sign could be assigned.

Weakly coordinating anions (WCAs) are important for academic reasons as well as for technical applications. Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−, a new WCA, is accessible by treatment of [GaCl3(dmap)] (dmap=4‐dimethylaminopyridine) with LiC2F5. The anion [Ga(C2F5)4]− proved to be reluctant towards deterioration by aqueous hydrochloric acid or lithium hydroxide. Various salts of [Ga(C2F5)4]− were synthesized with cations such as [PPh4]+, [CPh3]+, [(O2H5)2(OH2)2]2+, and [Li(dec)2]+ (dec=diethyl carbonate). Thermolysis of [(O2H5)2(OH2)2][Ga(C2F5)4]2 gives rise to a dihydrate of tris(pentafluoroethyl)gallane, [Ga(C2F5)3(OH2)2]. All products were characterized by NMR and IR spectroscopy, mass spectrometry, X‐ray diffraction, and elemental analysis. Furthermore, an outlook for the application of [Li(dec)2][Ga(C2F5)4] as a conducting salt in lithium‐ion batteries is presented.

Syntheses of salts containing the tris(pentafluoroethyl)stannate(II) ion, [Sn(C F ) ] , were achieved through deprotonation of the corresponding stannane, HSn(C F ) , as well as by direct pentafluoroethylation of SnCl with LiC F . 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(C F ) , whereas Si, Ge, Sn, P halides gave rise to oxidation processes yielding hypervalent [SnX (C F ) ] salts (X=Cl, Br, I). Moreover the unsymmetrical distannane, nBu SnSn(C F ) , was disclosed as an alternative precursor for the Sn(C F ) 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 [nBu Sn(D) ] and [Sn(C F ) ] ions was observed.

A versatile two-step synthesis of tris(pentafluoroethyl)stannane, HSn(C F ) , is presented. Electron-withdrawing C F groups significantly influence the polarity of the tin-hydrogen bond, which allows facile deprotonation of the compound, even in water. The utility of this electron-deficient stannane was illustrated in hydrostannylations of alkenes and alkynes, as well as in dehalogenation reactions. The remarkably high reactivity of HSn(C F ) is demonstrated in fast hydrostannylations, even in the absence of activators, whereby the regioselectivity of this process turns out to be solvent dependent. It is of great advantage that in dehalogenation reactions volatile halogenotris(pentafluoroethyl)stannanes, XSn(C F ) (X=I, Br), are formed that allow facile separation of the tin-containing byproducts from the reaction mixtures.

Schwach koordinierende Anionen (WCA) sind sowohl aus akademischen Gründen als auch für technische Anwendungen von hohem Interesse. Tetrakis(pentafluorethyl)gallat, [Ga(C2F5)4]−, ein neues WCA, ist durch die Reaktion von [GaCl3(dmap)] (dmap=4‐Dimethylaminopyridin) mit LiC2F5 zugänglich. Das Anion [Ga(C2F5)4]− zeigte gegenüber Salzsäure oder wässriger Lithiumhydroxid‐Lösung keine Zersetzung. Verschiedene Salze von [Ga(C2F5)4]− wurden mit den Kationen [PPh4]+, [CPh3]+, [(O2H5)2(OH2)2]2+ und [Li(dec)2]+ (dec=Diethylcarbonat) synthetisiert. Die Thermolyse von [(O2H5)2(OH2)2][Ga(C2F5)4]2 führt zum Tris(pentafluorethyl)gallan‐Dihydrat, [Ga(C2F5)3(OH2)2]. Alle Produkte wurden durch NMR‐ und IR‐Spektroskopie, Massenspektrometrie, Röntgenkristallstrukturanalyse und mittels Elementaranalyse charakterisiert. Ergänzend wird ein Ausblick für die Anwendung von [Li(dec)2][Ga(C2F5)4] als Leitsalz in Lithium‐Ionen‐Batterien gegeben.