Anionic halide complexes

Anionic guest inclusion compounds, 24 170 Anionic halide complexes, 24 540 Anionic initiators, 24 244-265 alkali metals, 24 245-248 alkyllithium compounds, 24 248-255 1,1-diphenylmethylcarbanions as,... 

Iron halides react with halide salts to afford anionic halide complexes. Because iron(III) is a hard acid, the complexes that it forms are most stable with F and decrease in both coordination number and stability with heavier halides. No stable I complexes are known. [FeF5(H20)]2 is the predominant iron fluoride species in aqueous solution. The [FeF6]3 ion can be prepared in fused salts. Whereas six-coordinate [FeClJ3 is known, four-coordinate complexes are favored for chloride. Salts of tetrahedral [FeClJ can be isolated if large cations such as tetraphenylarsonium or tetraalkylammonium are used. [FeBrJ is known but is thermally unstable and disproportionates to iron(II) and bromine. Complex anions of iron(II) halides are less common. [FeClJ2 has been obtained from FeCl2 by reaction with alkali metal chlorides in the melt or with tetraethylammonium chloride in deoxygenated ethanol. 

Basic dyes (triphenylmethane, xanthene, azine, etc., dyes) form ion-association compounds (ion-pairs) with anionic halide complexes of metals and non-metals e.g., SbCl, AuBr4 , TaFe , BF4 ). The resulting compounds, that may be extracted into non-polar organic solvents, may serve as a basis for sensitive spectrophotometric methods [62-65]. 

Mechanistic aspects of this catalytic process have been forthcoming from kinetic investigations of the component reactions which comprise the proposed cycle. The rate-limiting process in the catalytic cycle is the reaction between the anionic halide complexes. 

The late transition and main group metals follow the anodic oxidation pathway analogous to that in aqueous solutions. The minimal oxidation potentials in these cases can in fact be very low (up to max. 3.0 V), whUe higher ones are readily applied to accelerate the process. The anodic reaction consists of dissolution of metal ions in the form of anionic halide complexes, which are later transformed into insoluble alkoxides by reaction with alkoxide anions generated at the cathode, for example (Lehmkuhl, 1975) ... 

Pershina, V., Fricke, B., Kratz, J.V., Ionova, G.V. The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines. Radiochim. Acta 64, 37-48 (1994)... 

A variety of complexes of the thionyl imide anion [NSO] with both early and late transition-metal complexes have been prepared and structurally characterized. Since both ionic and covalent derivatives of this anion are readily prepared, e.g., K[NSO], McsMNSO (M = Si, Sn) or Hg(NSO)2, metathetical reactions of these reagents with transition-metal halide complexes represent the most general synthetic method for the preparation of these complexes (Eq. 7.10 and 7.11). ... 

Complexes of the sulfenamido anion [RSNR ] with several transition metals [Zr(IV), Ti(IV), Mo(VI), W(Vf), Ni(If), and U(IV)] are known.They are prepared by the reaction of the lithium derivative of the sulfenamido anion with a metal halide complex. A selenium complex W(N Bu)2( BuNSePh)2 has been obtained in a similar... 

Iron hydride complexes can be synthesized by many routes. Some typical methods are listed in Scheme 2. Protonation of an anionic iron complex or substitution of hydride for one electron donor ligands, such as halides, affords hydride complexes. NaBH4 and L1A1H4 are generally used as the hydride source for the latter transformation. Oxidative addition of H2 and E-H to a low valent and unsaturated iron complex gives a hydride complex. Furthermore, p-hydride abstraction from an alkyl iron complex affords a hydride complex with olefin coordination. The last two reactions are frequently involved in catalytic cycles. 

Thallium(i) salts have long been used in reactions with organic and organometallic halide complexes as a means of activating the halide by removal as insoluble T1X. However, the thallium ions proved not to be innocent bystanders, and numerous examples were reported in COMC (1995) where the metal-bound thallium complexes were formed. Deliberate reactions of thallium(i) and thallium(m) salts with metal carbonyl anions have yielded a variety of complexes of the form T1 MLJ3. In the past decade, new examples of metal carbonyl derivatives of thallium have been prepared (see Table 2). In addition, the propensity for Tl+ to form adducts with 16-electron noble metal complexes has been exploited. 

Syntheses from Diacetylide Anions and Metal-Halide Complexes... 

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