Actinide coordination number

Crystal Structure and Ionic Radii. Crystal stmcture data have provided the basis for the ionic radii (coordination number = CN = 6), which are summarized in Table 9 (13,14,17). For both and ions there is an actinide contraction, analogous to the lanthanide contraction, with increasing positive charge on the nucleus. 

Table 31.4 is a list of typical compounds of the actinides and demonstrates the wider range of oxidation states compared to lanthanide compounds. High coordination numbers are still evident, and distortions from the idealized stereochemistries which are quoted are again general. However, no doubt at least partly because the early actinides have received most attention, the widest range of stereochemistries is... 

The uncertainty of the proper coordination number of any particular plutonium species in solution leads to a corresponding uncertainty in the correct cationic radius. Shannon has evaluated much of the available data and obtained sets of "effective ionic radii" for metal ions in different oxidation states and coordination numbers (6). Unfortunately, the data for plutonium is quite sparse. By using Shannon s radii for other actinides (e.g., Th(iv), U(Vl)) and for Ln(III) ions, the values listed in Table I have been obtained for plutonium. These radii are estimated to have an uncertainty of 0.02 X ... 

The distribution of the observed higher borides among the five structural types (MB2, MB4, MBg, MB]2 and Mg ) presented in Table 1, which shows correlations with the metallic radius r. values of which are in order of decreasing magnitude (r, corresponds to coordination number 12). In order to discuss the existence of the actinide borides, the table also shows the unit cell volume V of the borides MB4, MBg and MB,2. 

The third category is the high coordination number lanthanides and actinides. The trivalent lanthanides show a decrease in with the progressive filling of the 4f orbitals, called the lanthanide contraction. Since the 4f orbitals are shielded by the filled 5s and 5p orbitals, the electronic configuration has no remarkable effect and therefore the variation in rM and an eventual change in coordination number and geometry determine the lability of the 1st coordination shell. 

A guiding principle for the solvent extraction chemist is to produce an uncharged species that has its maximum coordination number satisfied by lipophilic substances (reactants). Eor trivalent lanthanides and actinides (Ln and An, respectively), the thermodynamic data suggest a model in which addition of one molecule of TBP displaces more than one hydrate molecule ... 

This scheme of steps reflects the ability of some metals, like the trivalent actinides and lanthanides, to vary their coordination number since the trivalent Ln and An may go from 9 to 8 and, finally, back to 9. The last step reflects the operation of the third mechanism proposed for synergism. 

Although no single crystal X-ray work has been done on the cyclopentadienide complexes of the trivalent actinides, it is clear that they have structures similar to those of the known homologous lanthanides. Both the trivalent lanthanides and actinides behave as Lewis acids and form adducts to complete their coordination spheres. An optimum formal coordination number of ten is indicated and their structures seem to be dictated by a maximization of electrostatic interactions within the steric constraints of the ligands. 

From the relative stabilities of the actinide homoalkyls or -allyls and the tris(cyclopentadienyl) actinide alkyls, it appears that a coordinatively saturated metal center is necessary for kinetic stability. In contrast to f-transition metal alkyls, the absence of hydrogens appears to be of minor importance. In the case of the lanthanide alkyls and the tetrabenzylthorium, where the formal coordination number is only four, the steric bulkiness of the Hgands must be responsible for their observed thermal stability. 

Relatively few structural analysis of the decacoordinated lanthanide complexes have been reported. Although the lanthanides and actinides are long suspected as candidates for having decacoordination, it was not until 1965 that Lind, Lee and Hoard 211) were able to establish decacoordination for La(III) ion in monoclinic crystals of composition [La(EDTAH)] 7H2O. To date, only about ten or so decacoordinated structures are known, but many lanthanide complexes may have a coordination number of ten. 

Symbol Pa atomic number 91 atomic weight 231.04 an actinide series radioactive element an inner-transition metal electron configuration [Rn]5/26di7s2 valence states +4 and +5 atomic radius 1.63A (for coordination number 12) twenty-two isotopes are known in the mass range 215-218,... 

Symbol Th atomic number 90 atomic weight 232.04 an actinide series radioactive element electron configuration XRn]6d27s2 valence state +4 atomic radius 1.80 A ionic radius, Th4+ 1.05 A for coordination number 8 standard electrode potential, E° for Th4+ -1- 4e Th is -1.899V all isotopes are radioactive the only naturally-occurring isotope, Th-232, ti/2 1.4xl0i° year twenty-six isotopes are known in the mass range 212-237. 

Symbol U atomic number 92 atomic weight 238.029 an actinide series radioactive element heaviest naturally-occurring element electron configuration J Rn]5/36(ii7s2 valence states +2, -i-3, +4, -i-5, -1-6 ionic radii 1J3+ l.OSA, IJ4+ O.89A, 0.76A, for coordination number 6 and U 0.45 A and 0.81 A... 

Most transition metals of the three d-series in all their valency states exhibit ionic radii within the limits of 0.55 and 0.86 A, favourable to octahedral coordination. In fact higher coordination numbers are observed only in fluorides of the largest transition ions, above all in compounds of the lanthanide and actinide series. Therefore fluorides of those elements, though sometimes isostructural with compounds of the d-series, will not be discussed here. For information the books and reviews written by Spedding and Daane (291), Katz and Seaborg (181) and Kaiz and Sheft (182) may be consulted. 

The simplest of the cubic structures is the primitive cubic structure. This is built by placing square layers like the one shown in Figure 1.1 (a), directly on top of one another. Figure 1.9(a) illustrates this, and you can see in Figure 1.9(b) that each atom sits at the corner of a cube. The coordination number of an atom in this structure is six. The majority of metals have one of the three basic structures hep, cep, or bcc. Polonium alone adopts the primitive structure. The distribution of the packing types among the most stable forms of the metals at 298 K is shown in Figure 1.10. As we noted earlier, a very few metals have a mixed hcp/ccp structure of a more complex type. The structures of the actinides tend to be rather complex and are not included. 

Most commonly, metal ions M2+ and M3+ (M = a first transition series metal), Li+, Na+, Mg2+, Al3+, Ga3+, In3+, Tl3+, and Sn2+ form octahedral six-coordinate complexes. Linear two coordination is associated with univalent ions of the coinage metal (Cu, Ag, Au), as in Ag(NH3)2+ or AuCL Three and five coordination are not frequently encountered, since close-packing considerations tell us that tetrahedral or octahedral complex formation will normally be favored over five coordination, while three coordination requires an extraordinarily small radius ratio (Section 4.5). Coordination numbers higher than six are found among the larger transition metal ions [i.e., those at the left of the second and third transition series, as exemplified by TaFy2- and Mo(CN)g4 ] and in the lanthanides and actinides [e.g., Nd(H20)93+ as well as UC Fs3- which contains the linear uranyl unit 0=U=02+ and five fluoride ligands coordinated around the uranium(VI) in an equatorial plane]. For most of the metal complexes discussed in this book a coordination number of six may be assumed. 

Table 2 Coordination Numbers and Geometries of Actinide Compounds...

Although coordination number 8 cannot be regurded as common, the number of known compounds has Increased rapidly in recent years, so thai it is now exceeded only by four- and six-coordiration. The factors important in this increase can be traced largely to improved three-dimensional X-ray lechniques and to increased interest in ihe coordination chemistry oflanthanide and actinide elements (see Chapter 14). 

Only a few structures of thiocyanate complexes are known for the lanthanides and actinides, i.e. for Er,341 Th342 and U.343 They all contain terminal N-bonded NCS and have as an interesting aspect a high coordination number, e.g. as in [NEt4]4[Th(NCS)8].342... 

The extensive chemistry of amido complexes, and, more particularly, of alkylamido complexes, reveals that the planar form is almost invariably found, along with bridging amides (221). Much attention has been paid to the synthesis of metal amido complexes of early transition metals, lanthanides and actinides. The amido group, particularly where it is bulky, confers unusual low coordination numbers on the metals and can also produce materials with considerable kinetic stability toward attack by nucleophiles (42, 67). However, the relevance of this extensive and fascinating chemistry to nitrogen fixation is somewhat problematic. 

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