Organo-übergangsmetall-chemie hochfluorierter ligand-systeme

Preparation and crystal structure of [WCl2(cp)2]+2[W4F18]2–(cp =η-C5H5) containing the new binary tungsten(IV) fluoride anion [W4F18]2–

“…The metallocene, [WCl,(cp),], was treated with two equivalents of WF, [equation ( 3 We were surprised to find that compound 1 had been formed in reaction (3). In fact WF, is usually reduced to give WF,-(Wv),8 compound 2, rather than the [W4Fl8l2-anion (W").…”

“…73( 1) 72.9( 7) 109( 2) 71( 1) lOl(3) 72m 77m 70 (2) 112 (3) 71.9(6) 108 (2) are bridged by a two-co-ordinated F atom. Additionally there are three terminal F atoms co-ordinated to each tungsten atom.…”

Chemical Redox Agents for Organometallic Chemistry

“…161 162 The pentafluorides, EF 5 , are more difficult to handle (in part because of the formation of HF with water) but are stronger oxidants than the chlorides (SbF 5 will oxidize the less electron-rich triarylamines unaffected by SbCl 5 , section II.A.2.a.iii) and are less likely to give rise to halogenated byproducts. Accordingly, distillation of EF 5 (E ) As and Sb) onto solutions of [MX 2 Cp 2 ] (X ) Cl, M ) V, 163,164 ] and AgCl, i.e., that chloride abstraction occurs with Ag + even though oxidation is favored, and observed, with AsF 5 . 164 Moreover, the reaction between [ReCl 2 -Cp 2 ]Cl with a mixture of Ag[SbF 6 ] and SbF 5 gives [ReCl 2 Cp 2 ][SbF 6 ] 3 via abstraction of the chloride counteranion with Ag + and oxidation by the pentafluoride.…”

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

“…Cp 2 VCl 2 is readily oxidized to [Cp 2 V(AsF 6 ) 2 ][AsF 6 ] (150) in the presence of anhydrous HF using either AsF 5 or AgAsF 6 . 150 (161) has been prepared by an identical procedure. 154,155 Further reaction of 160 with excess trimethylaluminum leads to the tetramethyl derivative Cp*TaMe 4 in quantitative yield.…”