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Synthesis and Reactivity of Tris(pentafluoroethyl)gallium Compounds
Author(s) -
Niemann Mark,
Neumann Beate,
Stammler HansGeorg,
Hoge Berthold
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900486
Subject(s) - chemistry , adduct , medicinal chemistry , gallium , reactivity (psychology) , tris , thermal decomposition , chloride , lithium (medication) , nuclear magnetic resonance spectroscopy , inorganic chemistry , stereochemistry , organic chemistry , medicine , biochemistry , alternative medicine , pathology , endocrinology
The reaction of [GaCl 3 (OEt 2 ) n ] with LiC 2 F 5 surprisingly leads to the formation of the anion [Ga(C 2 F 5 ) 3 Cl] – . The obtained lithium and tetraphenylphosphonium salts are useful starting materials for new pentafluoroethylgallium compounds. [PPh 4 ][Ga(C 2 F 5 ) 3 Cl] was conveniently transformed into [PPh 4 ][Ga(C 2 F 5 ) 3 X] (X = F, Br, I) with HF, NaBr, and NaI. Treatment of [Li(OEt 2 ) n ][Ga(C 2 F 5 ) 3 Cl] with aqueous hydrogen chloride gives rise to the tris(pentafluoroethyl)gallane adduct [Ga(C 2 F 5 ) 3 {(OH 2 )(OEt 2 )}]. Thermolysis of [Li(OEt 2 ) n ][Ga(C 2 F 5 ) 3 Cl] affords another tris(pentafluoroethyl)gallane adduct, [Ga(C 2 F 5 ) 3 (OEt 2 )], which can be converted into [Ga(C 2 F 5 ) 3 (dmap)] (dmap = 4‐dimethylaminopyridine). [Ga(C 2 F 5 ) 3 (OEt 2 )] as well as [Ga(C 2 F 5 ) 3 (dmap)] react with [PPh 4 ]Cl to [PPh 4 ][Ga(C 2 F 5 ) 3 Cl] and with HF to [HDMAP][Ga(C 2 F 5 ) 3 F]. Both [Ga(C 2 F 5 ) 3 (OEt 2 )] and [Ga(C 2 F 5 ) 3 (dmap)] are precursors for the previously reported weakly coordinating anion [Ga(C 2 F 5 ) 4 ] – . Characterizations of the new compounds were carried out by NMR and IR spectroscopy, mass spectrometry, X‐ray diffraction and elemental analyses.