Nuclear Magnetic Resonance and Nuclear Waste Reprocessing. Geoffrey Vidick, Nouri Bouslimani and Jean F. Desreux

Coordination and Radiochemistry, Dept.of Chemistry, University of Liège,

Introduction General.

First approach : use of relaxivity

Acknowledgements

NpO2+ and PuO2

2+ and their complexes

Second approach: NMR spectroscopy of paramagnetic compounds

The authors thank Prof. M.J. Hudson and L.M. Harwood, Dr. R. StJ. Foreman and F. Lewis, University of Reading, U.K., for a gift of BTP, BTBP and BTTP ligands.Financial support from the Institut Interuniversitaire des Sciences Nucléaires of Belgium (IISN), the European Integrated Project EUROPART (FP6) and the ACTINET research network are gratefully acknowledged.

NMR is a hardly broached research field in actinide science. We showed that well resolved NMR spectra of actinides complexes can be obtained. NMR and relaxivity are useful techniques to determine the stoechiometry of complexes and to obtain information about solvation state. The dipolar paramagnetic shift is a powerful method allowing to find the solution structure and conformation of Ln and Ac complexes. These informations about the properties of complexes in solutions are helps to more understand the properties of selective extracting agent for the Ac/Ln separations.

Conclusions

Well-resolved 1H NMR spectra can be for obtained for NpO2+ and PuO22+ complexes despite relatively high electronic relaxation timesThe paramagnetic shifts induced by NpO2+ in the NMR spectrum of BTBP in anhydrous CD3CN are again essentially of dipolar origin even though aromatic systems are prone to favor electronic spins delocalization. There is an excellent correlation between the calculated and the experimental shifts.

ppm (t1) -20.0-15.0-10.0-5.00.0

-3.73

-5.78

-6.90

-9.26

-9.48

-10.72

-13.11

-17.39

-20.00

-20.90

-21.18

3.64

2.37

3.28

3.09

2.03

2.00

4.09

2.16

HCH3

HCH3

HCH2

HCH2

HCH2 HCH2

HCH2

Hφ

Hφ

N NN

NN N

N

N

CH3CN

free ligand

ppm (t1) -20.0-15.0-10.0-5.00.0

-3.73

-5.78

-6.90

-9.26

-9.48

-10.72

-13.11

-17.39

-20.00

-20.90

-21.18

3.64

2.37

3.28

3.09

2.03

2.00

4.09

2.16

HCH3

HCH3

HCH2

HCH2

HCH2 HCH2

HCH2

Hφ

Hφ

N NN

NN N

N

N

CH3CN

free ligand z

x

Hmeta

Hortho

Hpara

“CH3”

“CH3”

Stratégy for the Nuclear Fuel Cycle in th 21st Century.

N NN

NN N

N

N

Calixarenes

TBP

BTBP

The management of nuclear wastes remains a major problem for future generations, particularly the storage of highly radiotoxic wastes. The minor actinides [MA] are the main contributors of the long term radiotoxicity. The transmutation of MA leads to an important decrease in waste radiotoxicity but requires the separation of MA from the lanthanides [Ln] that are neutrophages. The partitioning of MA from Ln is particularly difficult because of trivalent Ln and actinides [Ac] have very similar properties.

In recent decades, a family of bis-triazine ligands were found to be remarkably selective extracting agents for the MA/Ln separation [1]. However, their effectiveness decreases on going from a central pyridine ring (BTP) to a bipyridine (BTBP) and finally to a terpyridine unit (BTTP).

We use several advanced NMR techniques in order to fully characterize Ac ions and their complexes.

The dispersion of the longitudinal relaxation time T1 of the solvent nuclei with the magnetic field (NMRD) yields information on the magnetic properties and on the dynamic behavior of paramagnetic species. The relaxation rates 1/T1,2 (or relaxivites) depend on (1) the solvation state, (2) the rotational correlation time τ r, (3) the electronic relaxation τsi and (4) the solvent exchange time τm.

60

1 . .

1, ,c

in sph

f B rT

1 1 1 1

i ic r s m

NMRD titrations are very useful for the determination of the stoechiometry of complexes. The relaxivity decreases when a ligand is added from paramagnetic centers until a plateau is reached when the complex is fully formed.

As illustrated in the figure in right, the BTP ligand form a tris-complexe, the BTBP ligand a more solvated bis-complex and only a soluble 1:1 complex can is formed with BTTP ligand in nitric acid media.

M

SR

r

The chemical shifts induced by paramagnetic ions depend on (1) the dipolar interaction between the nuclear spins and the unpaired electronic spins and/or (2) the contact contribution due to electronic spin densities delocalized into the ligand orbitals and thus on the partial covalency of the coordination bonds. The dipolar shift is a through space interaction between the magnetic moment of the paramagnetic metal ion of the nucleus. The NMR spectra of complexes of ligands with dipolar Yb3+ ions, we can deduce solution structure from a geometrical model.

z

y

x

Ln

H

z

y

x

z

y

x

Ln

H

23

13cos 1

12i ir

2 23

1 13cos 1 sin cos2

12 2i zz xx yy i xx yy i ir

G factor, Å-3

-0.006 -0.004 -0.002 0.000 0.002 0.004 0.006 0.008

Para

magn

etic

shift

, ppm

-10

-5

0

5

10

15

BTP forms highly compact and symmetric tris-complexes. These very crowded and stable structures are highly hydrophobic units which are very well extracted.

Eu3+ ClO4- salt

-5-4-3-2-10123456789101112131415f1 (ppm)

N

N N

N

N

N N

N

N

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

-4-3-2-1012345678910111213141516f1 (ppm)

CD3CN

NN

NN N

N

N

Rigid cyclohexenyl groups

HNO3 media

Only poorly extractible 1:1 species is formed in nitrate media with BTTP due to the competition between ntritate ions and BTTP ligand to metalic ions center.

-25-23-21-19-17-15-13-11-9-8-7-6-5-4-3-2-101234567891113f1 (ppm)

0.94

6.06

1.00

1.87

2.08

6.36

1.06

-23.

12

-6.5

9

-3.6

7

1.9

11.9

4

3.0

7

5.4

2

7.6

8

10.

27

10.

29

N N

N

N

N N

N

N

Déplacements paramagnétiques expérimentaux, ppm

-40 -30 -20 -10 0 10

Dé

pla

cem

en

ts p

ara

ma

gn

étiq

ue

s ca

lcu

lés,

pp

m

-40

-30

-20

-10

0

10

BTBP form less crowded, partially solvated, bis-complexes with enough room for a nitrate ion is able to penetrate the coordination sphere and to deform the structure.

NO3-