PUB - Publikationen an der Universität Bielefeld

The reaction of [GaCl3(OEt2)(n)] with LiC2F5 surprisingly leads to the formation of the anion [Ga(C2F5)(3)Cl](-). The obtained lithium and tetraphenylphosphonium salts are useful starting materials for new pentafluoroethylgallium compounds. [PPh4][Ga(C2F5)(3)Cl] was conveniently transformed into [PPh4][Ga(C2F5)(3)X] (X = F, Br, I) with HF, NaBr, and NaI. Treatment of [Li(OEt2)(n)][Ga(C2F5)(3)Cl] with aqueous hydrogen chloride gives rise to the tris(pentafluoroethyl)gallane adduct [Ga(C2F5)(3){(OH2)(OEt2)}]. Thermolysis of [Li(OEt2)(n)][Ga(C2F5)(3)Cl] affords another tris(pentafluoroethyl)gallane adduct, [Ga(C2F5)(3)(OEt2)], which can be converted into [Ga(C2F5)(3)(dmap)] (dmap = 4-dimethylaminopyridine). [Ga(C2F5)(3)(OEt2)] as well as [Ga(C2F5)(3)(dmap)] react with [PPh4]Cl to [PPh4][Ga(C2F5)(3)Cl] and with HF to [HDMAP][Ga(C2F5)(3)F]. Both [Ga(C2F5)(3)(OEt2)] and [Ga(C2F5)(3)(dmap)] are precursors for the previously reported weakly coordinating anion [Ga(C2F5)(4)](-). Characterizations of the new compounds were carried out by NMR and IR spectroscopy, mass spectrometry, X-ray diffraction and elemental analyses.