Actinides, oxidative addition

The most obvious future data needs concern the missing, uncertain, and conflicting data identified above. Additional experimental investigations are needed in the case of Fe(III) and Zr(IV) carbonate complexation, and in the case of the Sn(IV)/Sn(II) and the Se(0)/Se(-II) redox couples. The molecular structure of metal silicate complexes needs clarification in order to remove ambiguities in the speciation scheme of these complexes. A rather challenging topic concerns the supposed transformation of crystalline tetra-valent actinide oxides, AnOz(cr), to solids with an amorphous surface layer as soon as the An4+ ion hydrolyses. The consequences of such... 

Recently, the CO-EXtraction (COEX) process was proposed by AREVA-France (104). The COEX process initially coextracts all of the U and Pu, and subsequently splits them into a U stream and a Pu stream containing an equal amount of U. In addition, a hydrometallurgical co-conversion process is coinstalled in an integrated recycling plant, which produces homogenous mixed actinide oxides (105, 106). Thus, the PR is enhanced. 

Synthetic routes to compounds containing M-C o bonds are fairly obvious. Substitution of, e.g., Cl by CH, can be effected by treatment with LiCH3 or CH3MgBr. A number of reaction types mentioned in Chapter 9 - oxidative addition, reductive elimination, insertion and cyclometallation (Sections 9.6 and 9.7) - have their uses in preparative routes to M-C bonds. The formation of organo-compounds of the lanthanides and actinides is an area of growing interest. Preparative methods are similar to those for other ER species where E is of relatively low electronegativity, e.g. ... 

Mono(organo)nickel compounds, via oxidative addition, 8, 44 Monoorganotin hydroxides, preparation, 3, 850 Monoorganotin oxides, preparation, 3, 850 Mono(pentamethylcyclopentadienyl) actinide(IV) compounds, reactions, 4, 207 Mono(pentamethylcyclopentadienyl) lanthanide(III) compounds, synthesis and characteristics, 4, 66 Mono(pentamethylcyclopentadienyl) uranium(IV) sulfido complex, synthesis, 4, 207-208 Mono(phenoxy-aldehyde) trichlorides, with Zr(IV),... 

In simple oxides, the actinides are most stable in the +4 oxidation state the dioxides, An02, are known for all elements thorium through californium. Although the properties of Th02, U02, and Pu02 are especially important in nuclear technology, complex actinide oxides (oxides with one or more metal ions in addition to an actinide) are also important since they may be found as fission products in nuclear fuels and they are models for possible matrices in which nuclear wastes will be stored. 

Patricia L. Watson Tobin J. Marks Oxidative addition of alkanes by lanthanide and actinide compounds, respectively... 

Oxidative addition of organic halides to low-valent metal complexes generates reactive metal alkyls that can then be used in insertion, coupling, carbonylation-decar-bonylation and cyclization reactions for organic synthesis. These transformations can be made catalytic after development of the stoichiometric chemistry using the more stable metal alkyls. This section surveys the reactions of alkyl, aryl and acyl halides with transition metal complexes of the groups IIIA (lanthanides and actinides), IVA-VIII and IB. 

The reactivity of transition-metal complexes toward oxidative addition increases on going from right to left across a period and on going down a given triade.g., for the d -4-coordinated complexes. In general, one-electron oxidations are more common among the lanthanides, actinides and early transition metals, whereas two-electron oxidations are more common in the later transition metals. The d -Pt(0) and -Pd(0) complexes, e.g., are more reactive toward RX oxidative addition than toward oxidative addition, whereas the opposite is true for the other group VIII metal complexes. 

The remainder of this section will focus on true SBMs, which have been the subject of vigorous research. Despite the electron deficiency of early transition metal, lanthanide, and actinide complexes, several groups reported that some of these d f" complexes do react with the H-H bond from dihydrogen and C-H bonds from alkanes, alkenes, arenes, and alkynes in a type of exchange reaction shown in equation 11.32. So many examples of SBM involving early, middle, and late transition metal complexes have appeared in the chemical literature over the past 20 years that chemists now consider this reaction to be another fundamental type of organometallic transformation along with oxidative addition, reductive elimination, and others that we have already discussed. 

In comparison, group 9 metals can generate either the linear or the branched isomer, depending on the nature of the ancillary ligands and are thought to proceed by oxidative addition/syn-insertion/reductive elimination. Reactions of alkane thiols were achieved for the first time with Rh and later with Pd and actinides. Depending on the metal and ligand choice, either the branched or linear product can... 

This is a special volume of Inorganic Syntheses that focuses on complexes that are likely to be useful as starting materials for the preparations of new transition metal coordination and organometallic compounds. There are chapters on complexes with weakly coordinated and therefore easily displaced ligands, low-valent complexes that undergo oxidative-addition reactions, substituted metal carbonyl complexes, nucleophilic metal carbonyl anions, transition metal clusters, a variety of cyclopentadienyl complexes, lanthanide and actinide complexes, and a range of other useful ligands and complexes. 

The same process occurs with actinides and lanthanides for which only one-electron oxidation is possible. An example of such an oxidative addition is shown in Equation 7.10. Dissociation of an ether precedes the coordination of KX and halide abstraction. 

As discussed in Chapter 9, the insertion of olefins and alk)nes into metal-amido complexes is limited to a few examples. Such insertion reactions are proposed to occur as part of the mechanism of the hydroamination of norbomene catalyzed by an iridium(I) complex and as part of the hydroamination of alkenes and alkynes catalyzed by lanthanide and actinide metal complexes. This reaction was clearly shown to occur with the iridium(I) amido complex formed by oxidative addition of aniline, and this insertion process is presented in Chapter 9. The mechanism of the most active Ir(I) catalyst system for this process involving added fluoride is imknown. 

The hydroamination of olefins has been shown to occur by the sequence of oxidative addition, migratory insertion, and reductive elimination in only one case. Because amines are nucleophilic, pathways are available for the additions of amines to olefins and alkynes that are unavailable for the additions of HCN, silanes, and boranes. For example, hydroaminations catalyzed by late transition metals are thought to occur in many cases by nucleophilic attack on coordinated alkenes and alkynes or by nucleophilic attack on ir-allyl, iT-benzyl, or TT-arene complexes. Hydroaminations catalyzed by lanthanide and actinide complexes occur by insertion of an olefin into a metal-amide bond. Finally, hydroamination catalyzed by dP group 4 metals have been shown to occur through imido complexes. In this case, a [2+2] cycloaddition forms the C-N bond, and protonolysis of the resulting metallacycle releases the organic product. 

An additional overview is given below for preparing specific actinide oxides, and discussions on the preparation of actinide oxides are also provided in a recent chapter on the subject (Morss 1991). 

One final comparison can be made by looking at the oxides formed by Dy and Cf, which are electronic homologs. The oxide system of Dy is essentially that of Dy203, while with Cf, in addition to its sesquioxide, there are Cf70j2 and Cf02 (Cf02 is difficult to form, as is Tb02). Comparisons between other pairs of lanthanide and actinide oxides are also informative. 

Comparison of the nonrelativistic and scalar-relativistic results for fee Au reveals the large impact that relativity has on the lattice constant (6%) and bulk modulus (57%) [542]. The most important quaUtative change in the band structure of fee Au is the more than 2-eV lowering of the s-band relative to the bottom of d-bands. In addition, the overall width of the d-bands is increased by more than 15% due to a relativistic delocaUzation of the d- states. The spin-orbit coupling included LGGTO DFT-GGA calculations were made for fluorite structure actinide oxides MO2 (M=Th,U,Pu) and their clean and hydroxylated surfaces, [556], magnetic ordering in fee Pn [557] and bulk properties of fee Pb [558]. 

Metals with a d f" configuration, group 3 metals, lanthanides, and actinides, are usually classified as f-elements. Because they are highly electropositive, they form polarized bonds with p-block elements, including carbon and nitrogen. So far, two reaction mechanisms have been established for d f metals cr-bond metathesis, a 2o—2o process, and 1,2-addition, a [2ct—2jt] process (2cr stands for the two electrons involved in the transition state that come from a tr bond and 2jt indicates the two electrons involved in the transition state that come from a Jt bond) (Scheme 1). " Oxidative addition, another type of reaction mecharusm that is common for late transition metals, is absent from the chemistry of rare-earth metals or actinides. This is partly because of the lack of valence electrons, i.e., a d electronic configuration however, even for uranium, which has multiple accessible oxidation states, no genuine oxidative addition reactivity has been reported. The subject of C—H bond activation mediated by f-elements has been dis-cussed by several recent reviews. ... 

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