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24. SOLUTION CHEMISTRY of the LANTHANIDE ELEMENTS Gregory

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24. SOLUTION CHEMISTRY of the LANTHANIDE ELEMENTS Gregory .24. SOLUTION CHEMISTRY OF THE LANTHANIDE ELEMENTS Gregory R. Choppin Department of Chemistry Florida State University Tallahassee, Florida 32306,U.S.A. ABSTRACT Complexes of the lanthanide elements provide insight into the factors which are important in ionically bonded systems. The enthalpy and entropy terms of complexation are a measure of the role of hydration effects while the free energy measures the metal-ligand interaction. The role of ligand basicity in the nature of the complex as an inner sphere or a solvent- separated outer sphere species is reviewed. An equation which has been used successfully to calculate stability constants which agree with experimental values is described and shown to be useful in establishing models for lanthanide complexing. The stability of complexes as a function of canonical structure of organic ligands and of ligand ring size is discussed. A study of charge polarization in conjugated organic ligands complexed by lanthanide cations is described. .25. SOLUTION CHEMISTRY OF THE LANTHANIDE ELEMENTS I. INTRODUCTION The development of separation methods using ion exchange resins has provided chemists with large quantities of very pure individual lanthanide elements. As a result, in the last 30 years research in lanthanide chemistry has been relatively intensive and has led to a rather satisfactory understanding of the chemical behavior of these elements as well as to the growing utilization of them in a variety of technological applications. A central feature of lanthanide chemistry is the strongly ionic character of the bonding between lanthanide cations and other atoms. As a result of this ionicity, they can be classified as "hard" (strongly acidic) cations. This hard acid nature is evident whether we consider the bonds between lanthanide cations with oxygen/ nitrogen, or halogen donors in complexes in aqueous solution (1) or the metal-car Don bonds of organometallic compounds (2). Due to the ionic nature of the bonding, lanthanide cations do not display the restricted stereochemistry typical of the d transition elements. The coordination number and the geometry of the coordination sphere in the d elements are essentially determined by the overlap of the metal and ligand oroitals. However, in the ionic complexes of the lanthanides, the number and arrangement of the ligand donor atoms are the result of the interplay between steric and electrostatic factors. This leads to a range of observed coordination numbers from 5 to 12 for lanthanides in solid compounds. Knowledge of the coordination number of lanthanide cations in aqueous solution is very limited. Primary sphere hydration numbers of 8 and 9 have been reported from x-ray (3) and neutron (4) scattering. It is likely that even in complexes with polydentate ligands such as EDTA, the lanthanide cation remains .26. partially hydrated with a total coordination number of 8 to 10. However, direct experimental verification of such a model is lacking and only lower limits of the coordination number can ba established - e.g., 9 in the Ln(DP)3~ (DP » dipicolinate) complexes (5). In aqueous solution the hard nature of the lanthanide citicTiS excludes reaction with soft bases and restricts inter- action to F, O, and N donors. Moreover, the interactions usually cause minimal changes in the optical or magnetic spectra involving the f orbital electrons. This insensitivity deprives the chemist of techniques which have been of major importance in the study of transition element complexes. To offset this disadvantage is the fact that the absence of significant covalent effects allows simpler interpretation of lanthanide complexation data in many systems. For example, the predominance of pseudo- contacts shifts in the NMR spectra of lanthanide compounds is the basis of their use as shift reagents. Moreover, lanthanide complexation can be used to test models of electrostatic interaction. II. COMPLEXATION THERMODYNAMICS An extensive body of data exists on the thermodynamic changes (AG, AH, and AS) associated with lanthanide complexation. Plots of these functions vs. lanthanide atomic number (or, vs. the reciprocal of the radii of the cations) often show a relatively linear change in the free energy but definitely non- linear curves for the enthalpy and entropy changes. This typo of pattern is shown in Figure 1 for the reaction: The AH and AS curves are different in shape from the curve for AG but since both AH and AS are positive, in the expression &G « AH - TAS, the non-linearity largely cancels to produce an almost .27. linear AG function. This "compensation" in* the aH and AS values has a particular significance in the interpretation of the thermodynamic parameters of complexation. Complexation causes* a decrease in the hydration of the cations and anions, resulting in a positive entropy change. Since energy is required to break the cation-water and water-water interactions in the hydration sphere, such dehydration also results in a positive enthalpy change. The combination of the dehydrated cation and anion reduces the degrees of freedom (a negative contribution to the entropy) and forms an ionic bond (a negative enthalpy change). The experimental values of AH and AS reflect the sum of the opposed contributions of dehydration and cation-ligand combina- tion. Since the observed values of AH and AS for most lanthanide complexes are positive, it seems that the dehyration effects are more significant than the combination of ions in these terns. •800- MS •60.0 - •40.0 - _ «200 -AG 000- -20X)- o. ~°~-O -AM -400 - i I Pt I Pm I EM I Tb I to~l Tm I C« Hi Sm Gd L» Er Vb Figure 1. Variation of the values of the free energies, enthalpies, and entropies of complexation of lanthanide cation» forming Lni1*^ . .28. The observed compensation of the enthalpy and entropy changes can be related to this dominance of the dehydration contribution to the net values. The stepwise reactions can be written as: 3 (a) Ln(H2O)* - (n-p)H2O h-AGD' AV AS (b) (m-q)H2O 3 (c) Ln(H2O)* AGR, AHR, ASR (3) The net reaction is: 3 Ln(H2O)* + A(H2O)m + (n+m-p-q) HjO AG, AH, AS (4) The net thermodynamic change is: AG AG AHR) - ASR) (5) fl To explain the compensation effect between AH and AS, it is assumed that AG-'O. This has not been derived from first = principles but is a logical conclusion of AH_ TASD. It has been suggested that AG-=0 results from the fact that all hydrated species are always in equilibrium with the bulk solvent (6). We can go even further since the observation of positive values for AB and AS indicate that: |AHH| > |AHR| and |AS |AS H The consequence of this is that the observed entropy and enthalpy changes reflect primarily the sum of reactions 2(a) and 2(b) while the observed free energy change is related almost com* pletely to reaction 3. Based on these considerations, we can use the thermodynamic changes to describe both the hydrational .29. changes (from the AH and AS values) as well as the combination step (from the AG value) of the net complexation reaction. The principle involved in this model of the individual subreactions has been used also to identify innei and outer sphere complexation. In outer sphere formation, the cation retains its first sphere water and the cation and anion are thus separated by a water molecule. Since the dehydration in reaction 2(a) is minimal, the net enthalpy and entropy changes could be expected to be either negative or positive, but, in any case, small. The values for reaction 3 would be negative and small (due to the relatively large separation of the caticn and anion). Conversely, in inner sphere complexation, the cation hydration sphere is disrupted sufficiently to allow direct contact between the cation and the anion. As a result, the measured net AH and AS of the inner sphere complexation are expected to be positive and, also, larger in absolute value than for outer sphere formation. Based on this interpretation of the signs and absolute values of AH and AS of complexation, a predominantly outer sphere character has been assigned to the 1:1 lanthanide complexes with perchlorate, halides, nitrate, sulfonate, and trichloro- acetate ligands, and an inner sphere nature to the iodate, fluoride, sulfate, and acetate complexes (7). A correlation was noted between the nature of the complex and the pK cl value of the acidic ligand (a measure of the basicity of the ligand): Inner Intermediate Outer Ligand: Ac", F", ClAc", CljAc, CljAc", SCN", N03, Cl" pKa: 4.5, 4, 2.8, 1.0, -0.5, -1.8, -2.5, -2.7 We return to a more quantitative evaluation of the inner vs. outer sphere character correlation with ligand pK in a later section of this paper. .30. III. TEST OF AN IONIC MODEL The correlation of the free energy of coroplexation, AG, with the metal-ligand step, Equation 4, suggests that an equation describing ionic interaction may be useful in estimating the AG values. The Born equation calculates the free energy of inter- action of a cation of charge Z and an anion of charge Z. at an intemuclear distance d,- in a solvent of dielectric constant Deff Z1Z2 AG Munze (8) has proposed such an equation expanded to include a "cratic" term (for the change in the number of species when M + X combine to give MX) and a DeBye-Huckel term for activity coefficient correction when the ionic strength, \x , is not zero, The full equation is: Ne - RT'vln 55.51 + RTILnf, . (u) (6) effdd1,2 where N » Avogadro's number; e - 4.80 x IO*"*"1100 esu; cation and anion ionic radii; v • -1. 2 ELnf(w) - -AZ ^ Dp with AZ2 ""CAZ MA" (ZM * Zl)^} a-4*3J B" °-33' c" °-75? D" °-15- Munze used the bulk value of the dielectric constant with a tempera- ture dependent term.
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