Coordination Chemistry of Actinide and Lanthanide Ions

66 Pages·2001·1.03 MB·English

Coordination Chemistry of Actinide and Lanthanide Ions

Ildikó Farkas

Doctoral Thesis
Stockholm 2001



Department of Chemistry
Inorganic Chemistry
Royal Institute of Technology
S-100 44 Stockholm, Sweden

Department of Chemistry
Inorganic Chemistry
Royal Institute of Technology
S-100 44 Stockholm, Sweden


Coordination Chemistry of Actinide and Lanthanide Ions

Ildikó Farkas

AKADEMISK AVHANDLING
som med tillstånd av Kungliga Tekniska Högskolan framlägges till offentlig granskning
för avläggande av filosofie doktorsexamen i oorganisk kemi, fredagen den 26 oktober
2001, kl 14.00 i K2, KTH. Fakultetsopponent är Professor Staffan Sjöberg. Avhandlingen
försvaras på engelska.

Abstract
Water exchange of the actinide ions, U(IV), U(VI) and Th(IV), in 4 m NaClO media as
4
well as coordination chemistry of lanthanide(III) ions with the glycolate ligand are discussed in this
thesis.
The activation parameters for the water exchange reaction of UO 2+(aq), U4+(aq), UF3+(aq)
2
and a lower limit for the water exchange rate constant at room temperature for Th4+(aq) have been
determined by 17O NMR relaxation techniques. For the paramagnetic U4+(aq) and UF3+(aq) ions,
the water exchange was studied directly, while for the diamagnetic UO 2+(aq) and Th4+(aq),
2
Tb3+(aq) was used as a chemical shift reagent. The results for UO 2+ are in fairly good agreement
2
with other kinetic data. It is interesting to note that in contrast to UO 2+, the rate of water exchange
2
on U4+ is not significantly influenced by ligands as OH- or F-. Based on the known coordination
geometry of UO 2+(aq) and also using information obtained in quantum chemical calculations, an
2
associative or interchange mechanism was suggested for the water exchange in UO 2+(aq). The
2
calculated activation energy is in agreement with the experimental data. Since the coordination
number of water in U4+(aq) is uncertain, 9 or 10, it is rather difficult to make propositions about the
mechanism of the water exchange for this ion. However, the experimental data indicate an
interchange mechanism.
The complexation at high pH between glycolate and different lanthanide(III) ions, Sm3+,
Eu3+, Dy3+, Er3+ and Lu3+ has been studied by potentiometry and spectroscopic techniques. Based
on this information a series of di- and tetranuclear ternary complexes were identified. By
combination of the experimental information from solid-state structures, spectroscopy and
potentiometry, the proposed constitution of these complexes are
[Ln (OCH COO) (HOCH COO) (H O) ]2- and [Ln (OCH COO) (OCH COO) (HOCH COO) ]-x,
2 2 2 2 4 2 x 4 2 4 2 x 2 4-x
with x = 2-4. The oxyacetate is formed by deprotonation of the α-OH group in the glycolate as a
result of the very strong inductive effect of the metal ion. The “Ln (OCH COO) ” unit has a cubane
4 2 4
like structure where the oxy group act as a bridge between three Ln atoms.
A structure study is also part of the work, providing supporting information about the
formation of oxyacetate complexes. The crystal structure of the sodium salt of the uranyl-
oxyacetate-fluoride dimer, Na (UO ) (OCH COO) F ·6H O as well as that of some lanthanide-
4 2 2 2 2 4 2
glycolates, Lu(HOCH COO) ·2H O and Dy (OCH COO) (HOCH COO) ·4H O, have been
2 3 2 2 2 2 2 2 2
determined by single crystal X-ray diffraction. In the Dy (OCH COO) (HOCH COO) ·4H O
2 2 2 2 2 2
structure with a dysprosium-oxyacetate dimer core, the dysprosium ions have a coordination
number of eight and the geometry is distorted dodecahedral. The structure consists of a three-
dimensional network of cross-linked metal-ligand chains, while the other lanthanide crystal,
Lu(HOCH COO) ·2H O, consists of discrete eight-coordinated cationic Lu(HOCH COO) (H O) +
2 3 2 2 2 2 4
and anionic Lu(HOCH COO) - complexes.
2 4

Keywords: water exchange, dynamics, uranium(IV), uranyl, thorium(IV), aqua ions, fluoride, 17O
NMR relaxation techniques, terbium(III), potentiometry, lanthanides, glycolate, α-OH group,
deprotonation, X-ray crystallography, TRLFS, NMR.

Preface
This work was started at Inorganic Chemistry, KTH as a joint venture with
the Physical Chemistry Department, Lajos Kossuth University (KLTE), Debrecen,
Hungary. I entered the project at the KLTE in September 1996, and one year later I
continued it at the Department of Chemistry, Inorganic Chemistry, Royal Institute
of Technology, Stockholm. My supervisors at that time were István Bányai and
Professor Ingmar Grenthe. I took the licentiate exam in 1999 based on the water and
electron exchange studies; the latter one is not part of this doctoral thesis. After one-
year break in 2000 I started to work with potentiometry at the KTH under Prof.
Ingmar Grenthe’s and Dr. Zoltán Szabó’s supervision. The thesis is based on the
following publications:

Paper I “Rates and Mechanisms of Water Exchange of UO 2+(aq) and
2
UO (oxalate)F(H O) -: A Variable Temperature 17O and 19F NMR
2 2 2
Study.”
Ildikó Farkas, István Bányai, Zoltán Szabó, Ulf Wahlgren and Ingmar
Grenthe
Inorg. Chem. 2000, 39(4), 799

Paper II “The Rates and Mechanisms of Water exchange of Actinide Aqua
Ions: A Variable Temperature 17O NMR study of U(H O) 4+,
2 10
UF(H O) 3+, and Th(H O) 4+.”
2 9 2 10
István Bányai, Ildikó Farkas and Ingmar Grenthe
J. Phys. Chem. A 2000, 104, 1201

Paper III “Crystal structure of the sodium salt of the uranyl-oxyacetate-fluoride
dimer, Na (UO ) (OCH COO) F ·6H O.”
4 2 2 2 2 4 2
Ildikó Farkas, Ingeborg Csöregh and Zoltán Szabó
Acta Chem. Scand. 1999, 53, 1009
Paper IV “Crystal structure of some lanthanide(III)-glycolate complexes,
Lu(HOCH COO) ·2H O and Dy (OCH COO) (HOCH COO) ·4H O.
2 3 2 2 2 2 2 2 2
An X-ray Diffraction and Vibrational Spectroscopic Study.”
Ildikó Farkas, Andreas Fischer and Martin Lindsjö
submitted to J. Chem. Soc., Dalton Trans.

Paper V “Complexation of Cm(III) and lanthanide(III) ions by glycolic acid:
TRLFS, potentiometric, vibrational and NMR spectroscopic studies.”
Thorsten Stumpf, Ildikó Farkas, Thomas Fanghänel, Zoltán Szabó and
Ingmar Grenthe
under way
Table of Contents
I Introduction 1
II Water Exchange on Actinide Ions 4
II.1 Background 4
II.1.1 General remarks 4
II.1.2 Previous studies on the water exchange of uranyl ion 5
II.2 Experimental methods 6
II.2.1 NMR relaxation techniques 6
II.2.2 Determination of activation parameters 10
II.3 Study on the water exchange of actinide ions 11
II.3.1 An important parameter: the coordination number of aqua ions 11
II.3.2 Conclusions 13
III Coordination Chemistry of Lanthanide(III)-, Uranyl- and Actinide(III)-
Glycolate Systems 20
III.1 General remarks 20
III.2 Previous studies on the complexation of uranyl and
lanthanide(III) with glycolate ligand 21
III.2.1 Complexation of glycolate with uranyl ion 22
III.2.1 Complexation of glycolate with lanthanide(III) ions 22
III.3 Potentiometric study on lanthanide(III)-glycolate systems 23
III.3.1 Experimental background 23
III.3.1.1 Solution chemical equilibrium 23
III.3.1.2 Equilibrium analysis by potentiometry 23
III.3.1.2.1 Measurement of [H+] with glass electrode 24
III.3.1.2.2 Equilibrium calculations in a three-component
metal-ligand-proton system 25
III.3.1.2.3 A special case: a three-component system reduced
to two components 28
III.3.1.3 Activity coefficients 30
III.3.2 Potentiometric titration results in lanthanide-glycolate systems 32
III.4 Spectroscopic studies on lanthanide(III)- and actinide(III)-
glycolate solutions 35
III.4.1 Time resolved laser fluorescence spectroscopic study of
actinide(III)-glycolate solutions 35
III.4.2 Vibrational spectroscopic measurements in Dy(III)-
glycolate solutions 37
III.4.3 Lu(III)-glycolate solutions studied by NMR spectroscopy 37
III.5 Crystallographic study on lanthanide(III)- and uranyl-
glycolate complexes 39
III.5.1 Crystal structure of a uranyl-oxyacetate-fluoride dimer 40
III.5.2 Crystal structure of some lanthanide(III)-glycolate
and oxyacetate complexes 42
III.5.2.1 Crystal structure of Lu(HOCH COO) ·2H O 42
2 3 2
III.5.2.2 Crystal structure of Dy (OCH COO) (HOCH COO) ·4H O 44
2 2 2 2 2 2
III.6 Constitution and structure of the lanthanide-
glycolate/oxyacetate complexes 46
IV Conclusions and Future Work 48
References 50