Actinide complexes halides

A wide variety of anionic actinide halide complexes are well known and typically are isolated with alkah or aUcahne-earth metal ions. The tendency and stability ofthe anionic complexes follow the trend F > Cl > Br I. The bivalent fluorides and... 

Phosphine oxide. Many reported actinide-phosphine oxide adducts are those of the actinide halide complexes (see Table 29). Most are obtained by direct reaction of the two constituents in nonaqueous media. UCl5(OPPh3) has been structurally characterized the coordination environment is best described as approximately octahedral. 

A wide variety of anionic actinide halide complexes are well known and typically are isolated with alkali or alkahne-earth metal ions. The tendency and stability of the anionic complexes follow the trend F Cl > Br I. The trivalent fluorides and chlorides typically form complexes of the form AnX4 and AnXe ". Plutonium has also been shown to give the following complexes PuCb ", Pu2Cl7, and PuClg . The anionic tetravalent actinide fluorides represent a broad class of complexes, for example, M AnFj, (x = 1, y = 5 x = 2, y = 6 V = 3, y = 7 x = 4, y = 8). Tetravalent actinide chloro, bromo and iodo complexes can be isolated from aqueous solutions in the form of octahedral AnCle " ions. 

Table 21.6 Stability of actinide halide complexes in aqueous solution. The values refer to perchlorate media and 25°C, if not otherwise staled. ...

The Absorption Spectra and Excited State Relaxation Properties of Lanthanide and Actinide Halide Vapor Complexes. I. ErCl3(AlCl3L, W.T. Camall, J.P. Hessler, H.R. Hoekstra, and C.W. Williams, J. Chem. Phys. 68, 4304-4309 (1978). 

Analysis of the Absorption Spectra of Complex Pentavalent Actinide Halides. LiUF6, o -NaUF6 and CsUFg. H.G. Hecht, J.G. Malm, J. Foropoulus, and W.T. Camall, J. Chem. Phys. 84, 3653-3662 (1986). 

The. applications of ion-exchange chromatography are exemplified by the selection shown in table 4.18. Among the most notable are the separation of lanthanides and actinides using a citrate, lactate or EDTA eluting agent the separation of many metals as halide complexes on anionic resins and the separation of amino-acids with citrate buffers. The use of pressurized systems for complex mixtures is likely to become more widespread in the future. 

The succeeding actinides (Cm, Bk, Cf, Es, Em, Md, No, Lr) mark the point where the list of isolated compounds tends to involve binary compounds (oxides, halides and halide complexes, chalcogenides, and pnictides) rather than complexes. Those studies of complexes that have been made are usually carried out in solution and, from Em, onwards, have been tracer studies. 

The best-studied aqueous actinide halide systems are the fluorides and the chlorides. Fluoride and chloride ions are added to the actinyl centers in a stepwise fashion (Scheme 4). The end member in the actinyl fluoride system is the pentafluoride, An02F5 . For the uranyl analog, the U = O and U-F bond distances were found to be 1.79 and 2.18A respectively. The uranium tetrafluoride ion, U02F4 , has been isolated as a dimer with two bridging fluoride ligands. The U = O, U-Fterminai, uud U-Fbridging distauces for this complex were found to be 1.79, 2.15 to 2.20 A, and 2.30 A, respectively. 

Actinide halides and oxyhalides are known to form numerous complexes with oxygen and nitrogen donor ligands and the preparation and properties of such compounds have recently been reviewed (12, 13). Relatively few protactinium halide complexes are known, but this situation reflects the lack of research rather than a tendency not to form complexes. However, there is sufficient information available for certain ligands to permit a comparison with the behavior of other actinide halides, and to illustrate the similarities and differences observed with the tetrahalides of thorium to plutonium inclusive and, to a lesser extent, with the protactinium and uranium pentahalides. 

DMSO) complexes (18) are relatively unstable toward oxidative decomposition. The known complexes are listed in Table X, together with infrared data, and are compared with the complexes formed by other actinide halides in Table XI. The protactinium(IV) complexes have been prepared by reacting the anhydrous halide with the appropriate ligand in nonaqueous, oxygen-free solvents such as methylene dichloride, chloroform, or methyl cyanide. 

The preparation and properties of halides of the actinides have been described fully. As most of these complexes are solid state, rather than molecular in nature, only overview information on classes of compounds will be provided. Adducts of the halide complexes will be discussed in the context of compounds of the respective Lewis bases vide infra). 

Arsines. The ligand o-phenylenebis(dimethylarsine) (diars) has been used to complex actinide halides. The complexes PaCl4(diars) and UCl4(diars) have been reported. Both are produced by the reduction of pentavalent precursors in solution upon addition of the arsine. ... 

As in the presence of aqua complexes, the presence of crown ethers facilitates the crystallization of actinide halide solvate complexes in this manner ThCl4(EtOH)3(H20) 18-crown-6 and ThCl4(MeOH)2(H20)2 15-crown-5 have been isolated. " ... 

The trivalent transplutonium halides have been extensively studied. Several reviews deal specifically with actinide halides. " In aqueous solution the mono- and bis-complexes have been characterized, with the formation of the latter decreasing down the halide series. For example, AmF and AmF2" have been studied, but only a very weak monochloride complex AmCP has been reported. These species are reported to have coordination numbers as high as 11, although recent EXAFS studies show that the hydration number decreases with increasing halide concentration (and ionic strength) at concentrations below which the halo complexes form. These data suggest the coordination numbers of the mixed aquo halo complexes are probably seven to ten. 

The immense number of chemical compounds formed by the halogens provides chemists with an extraordinary database from which numerous chemical and physical phenomena can be correlated with respect to various periodic trends. From databases like Inorganic Crystal Structure Data (ICSD, http //www.fiz-karlsruhe.de ) and International Centre for Diffraction Data (ICDD, http //www.icdd.com) with 67 000 and 25 000 entries, respectively, one can easily make out that halides are one of the dominant classes of compounds besides oxides. Even within the subset of inorganic solids, there is tremendous diversity of composition, structure, and properties and to summarize this would create its own encyclopedia. Therefore, the discussion in this article is limited primarily to binary halides, their structures, and some of their properties, except halides of elements which are nonmetals. Binary actinide halides are discussed elsewhere see Actinides Inorganic Coordination Chewistif. Complex halides (solid phases containing two or more kinds of metal ions), ... 

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