Neodymium hydration number

It has always been assumed that the hydration numbers for the lanthanides are higher than six, probably between 8 and 10, in analogy with the presence of enneaaquo ion [M(OH2)9 +] in neodymium bromate and ethylsulphate (see later, p. 121). Lanthanide hydration numbers have not been rigorously established, but some attempts have been made to study the problem by NMR technique (13—15). It is rather unfortunate that only low value for the hydration numbers ( 6) have been obtained, except for Er(III) and Yb(III) ions (756), where the hydration number is seven. 

Mioduski and Siekierski (1975) proposed that the structural changes occurred by a gradual displacement of a water molecule from the primary hydration sphere of the ions as the series proceeded from neodymium through terbium. This displacement leads to configurations with fractional hydration numbers for the Nd-Tb cations as the displaced water molecule belongs partially to the inner hydration sphere and partially to the outer hydration sphere. This explanation is consistent with the optical spectral observations of Geier and Karlen (1971) and the NMR data of Reuben and Fiat (1969) which gave no indication for an equilibrium between different hydration forms. 

The only complexes of lanthanum or cerium to be described are [La(terpy)3][C104]3 175) and Ce(terpy)Cl3 H20 411). The lanthanum compound is a 1 3 electrolyte in MeCN or MeN02, and is almost certainly a nine-coordinate mononuclear species the structure of the cerium compound is not known with any certainty. A number of workers have reported hydrated 1 1 complexes of terpy with praseodymium chloride 376,411,438), and the complex PrCl3(terpy)-8H20 has been structurally characterized 376). The metal is in nine-coordinate monocapped square-antiprismatic [Pr(terpy)Cl(H20)5] cations (Fig. 24). Complexes with a 1 1 stoichiometry have also been described for neodymium 33, 409, 411, 413, 417), samarium 33, 411, 412), europium 33, 316, 411, 414, 417), gadolinium 33, 411), terbium 316, 410, 414), dysprosium 33, 410, 412), holmium 33, 410), erbium 33, 410, 417), thulium 410, 412), and ytterbium 410). The 1 2 stoichiometry has only been observed with the later lanthanides, europium 33, 411, 414), gadolinium, dysprosium, and erbium 33). 

Hydrates of rare earth chlorides also have two different crystal systems a triclinic system for lanthanum, cerium, and praseodymium, as well as a monoclinic system for neodymium to lutetium and yttrium. CeCl3-7H20, as an example of the former system, is different from the above infinite polymer as two cerium atoms are connected by two [i2-bridges to form a dimer. The formula for this dimer is [(H20)7Ce([i2-Cl)2Ce(H20)7]Cl4 as shown in Figure 1.18. Therefore, the coordination number of cerium is nine and the polyhedron takes on a destroyed mono-capped square antiprism configuration. 

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