[(CF₃)₂Hg(μ‐F)₂Hg(CF₃)₂]²⁻ – Synthese, Struktur und Reaktivität

Abstract

Aktiviert durch Fluorid ‐ aus Hg(CF3)2 und TAS‐Fluorid (Me2N)3S+(Me3Si)F2− wurde der erste Komplex mit einem Fluoroquecksilberanion, [(Me2N)3S+]2[(CF3)2(μ‐F)2Hg(CF3)2]2−, hergestellt und röntgenographisch charakterisiert (Struktur des Anions im Kristall siehe rechts). Die Anionen eignen sich ‐ anders als die Neutralverbindung ‐ zur nucleophilen CF3‐Übertragung.

Fluoride ion transfer and stabilisation of reactive ions

“…Purely inorganic and more or less organic sulfur, phosphorus and carbon acceptors with a higher Lewis acidity than Me 3 SiF were transformed into fluoro anions. With this reagent F À transfer even to organometallic centers is possible, as has been shown by the isolation of (TAS þ ) 2 [(CF 3 ) 2 HgF] 2 [102] or TAS þ [Cp 3 NdFNdCp 3 ] À [103]. Fluoride ion catalysed reactions were investigated and highly reactive ''naked'' inorganic and organic anions were generated by Si-element bond cleavage.…”

Trimeric Perfluoro‐ortho‐phenylenemercury: A Versatile Lewis Acidic Host

“…In addition to cooperative effects arising from the proximity of the mercury( II ) centers, the electron‐withdrawing properties of the backbone and the accessibility of the mercury centers convey unusual Lewis acidic properties to the molecule 11. The importance of this electronic effect is nicely illustrated by the relative halophilicity of 1 and that of its non‐fluorinated analogue trimeric ortho ‐phenylenemercury ([( o ‐C 6 H 4 Hg) 3 ]) 12.…”

Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block Metals

“…Treatment of 308 with NSF 3 provides NSF 2 (CF 3 ) which was previously inaccessible (eq 100). The presence of fluoride ion in 308 leads to labilization of the Hg−C( CF 3 ) bond . In contrast Hg(CF 3 ) 2 cannot be used for nucleophilic transfer of CF 3 - due to the very strong Hg−C bond.…”