Studies on the Interaction of a Novel 6,6¿¿- bis(1,2,4-triazin-3-yl)-,2¿:6¿,2¿¿-terpyridine Ligand with Lanthanide(III) Ions and Americium(III)

(1)

Studies on the Interaction of a Novel

6,6’’-bis(1,2,4-triazin-3-yl)-2,2’:6’,2’’-terpyridine

Ligand with Lanthanide(III) Ions and

Americium(III)

F. W. Lewis, L. M. Harwood, M. J. Hudson, M. G. B. Drew, G.

Modolo, M. Sypula, J. F. Desreux, N. Bouslimani and G. Vidick

1

st

_{ACSEPT International Workshop}

ITN Headquarters

Lisbon

(2)

Introduction

BTPs

N N N N N N N R R R R N N N N N R R N N N R R

BTBPs

N N N N N N N N

CyMe

₄

-BTBP

(3)

Introduction

N N N N N R R N N N N R R N N N N N N N N N

CyMe

₄

-BTTP

BTTPs

(4)

Synthesis of CyMe

₄

-BTTP

17 %

N N N N N N N N N N N N N+ N N+ O -O -N N N NC CN N N N N H₂ N H₂ N N NH2 NH₂ O O m-CPBA DCM Me₃SiCN Me₂NCOCl DCM N₂H₄ DMSO Et₃N THF, Δ

99 %

71 %

(5)

X-Ray Crystal Structure of CyMe

₄

-BTTP

(6)

Solvent Extraction Studies

Extraction of Am(III) and Eu(III) from HNO

₃

by CyMe

₄

-BTTP (0.01 M) in 1-octanol

0 1 2 3 4 1E-3 0.01 0.1 D_Am D_Eu 1 10 100 SF_Am/Eu [HNO₃] Initial D M (III) SF Am/ E u

(7)

Solvent Extraction Studies

0.00 0.05 0.10 0.15 0.20 1E-3 0.01 0.1 1 10 D_Am D_Eu 1 10 SF_Am/Eu D M (III) [HNO₃] Initial SF Am/ E u

Extraction of Am(III) and Eu(III) from HNO

₃

by CyMe

₄

-BTTP (0.01 M) + 2-bromohexanoic

(8)

Solvent Extraction Studies

0 1 2 3 4 1E-3 0.01 0.1 1 D_Am D_Eu [HNO₃] Initial 1 10 SF_Am/Eu SF Am/ E u D M (III)

Extraction of Am(III) and Eu(III) from HNO

₃

by CyMe

₄

-BTTP (0.01 M) + DMDOHEMA

(9)

Metal Complexes of CyMe

₄

-BTTP

CyMe

₄

-BTTP (1 eq) + Y(ClO

₄

)

₃

(0.5 eq)

in DCM/CH

₃

CN

Yttrium(III)

complex:

(10)

Solution-Phase NMR Studies of

Lanthanide Complexes

[terpyBTP]/[Gd3+] 0.0 0.5 1.0 1.5 2.0 2.5 Relax iv it y , s -1 mM -1 0 1 2 3 4 5

Nuclear Magnetic Relaxation Dispersion Titration

of Gd3+ _{by CyMe}

4-BTTP in anhydrous CD3CN (▲ =

(11)

Mass Spectrometry Studies of

Lanthanide Complexes

460.19 612.33 634.31 0.0 0.2 0.4 0.6 0.8 1.0 1.2 300 400 500 600 700 800 900 1000 1100

Electrospray Mass Spectrum of a CyMe₄

-BTTP:Gd(ClO₄)₃ mixture (2.5:1 ratio)

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Mass Spectrometry Studies of

Lanthanide Complexes

458.856145 459.189621 459.522918 459.856934 460.190033 460.524571 460.857932 461.192367 461.526257 461.860732 +MS, 0.0-0.5min #(2-20) 0 1 2 3 5 x10 Intens. 457 458 459 460 461 462 m/z 458.872120 459.206032 459.539620 459.873484 460.207033 460.541083 460.874529 461.208586 461.542808 461.877074 C74 H82 N18 Gd ,1380.62 0 500 1000 1500 2000 Intens. 457 458 459 460 461 462 m/z

Expanded view of the mass peak at m/z = 460.19

Computer simulation of the isotope distribution pattern of

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612.36 634.34 909.27 0.0 0.5 1.0 1.5 2.0 2.5 200 400 600 800 1000 1200 1400 1600 1800

Mass Spectrometry Studies of

Lanthanide Complexes

Electrospray Mass Spectrum of a CyMe₄

-BTTP:Yb(NO₃)₃ mixture (1:1 ratio)

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905.3 906.3 907.3 908.3 909.3 910.3 911.3 912.3 0 1 2 3 4 5 6 4 x10 Intens. 900 902 904 906 908 910 912 914 916 m/z 905. 258360 906. 2 60012 907. 260621 908. 26235 2 909. 2630 2 910. 2 65553 9 11. 266 604 912. 269138 913. 2 71704 YbC37H41N11O6 ,909.26 0 500 1000 1500 2000 Intens. 902 904 906 908 910 912 914 m/z

Mass Spectrometry Studies of

Lanthanide Complexes

Expanded view of the mass peak at m/z = 909.27

Computer simulation of the isotope distribution pattern of

(15)

Solution-Phase NMR Studies of

Lanthanide Complexes

1_{H NMR spectrum of a 2:1 mixture of CyMe}

4-BTTP

and Eu(ClO₄)₃ in anhydrous CD₃CN at 25 o_C

●= pyridine protons

+

= methyl protons

(16)

Solution-Phase NMR Studies of

Lanthanide Complexes

Expanded view of the methylene resonances in the1_{H NMR}

(17)

Solution-Phase NMR Studies of

Lanthanide Complexes

4-BTTP

and Yb(ClO₄)₃ in anhydrous CD₃CN at 25 o_C

+

(18)

Solution-Phase NMR Studies of

Lanthanide Complexes

Expanded view of the methylene resonances in the1_{H NMR}

(19)

Optimized Solution Structure

of Ytterbium bis-Complex

Two views of the optimized structure of Yb(CyMe₄-BTTP)₂3+ _obtained

by force-field calculations. The two square faces of the square antiprism are shown in red.

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(

)

2

(

)

2 3

1

1 3cos

1 sin

cos 2

12

2

i zz xx yy i xx yy i i

r

δ

χ

θ

χ

θ

ψ

π

⎡

⎛

⎞

⎤

=

_⎢

_⎜

−

+

_⎟

− +

−

_⎥

⎝

⎠

⎣

⎦

δ

_i = induced paramagnetic shift of nucleus i

χ

_xx,

χ

_yy and

χ

_zz = magnetic susceptibility terms

r

_i,

θ

_i and

ψ

_i= polar coordinates of proton i

Induced paramagnetic shifts calculated from:

Optimized Solution Structure

of Ytterbium bis-Complex

(21)

Experimental paramagnetic shift, ppm -30 -20 -10 0 10 20 30 40 Calculat ed param a gent ic shif t, ppm -30 -20 -10 0 10 20 30 40

Correlation between the calculated and experimental

paramagnetic shifts in the 1_{H NMR spectrum of [Yb(CyMe}

4

-BTTP)₂(ClO₄)₃]. 99 % intervals indicated by dotted lines.

Optimized Solution Structure

of Ytterbium bis-Complex

(22)

Solution-Phase NMR Studies of

Lanthanide Complexes

4-BTTP

and Yb(NO₃)₃ in anhydrous CD₃CN at 25 o_C

+

x = methylene protons

■= free ligand ■

(23)

Experimental paramagnetic shift, ppm -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 C a lculated pa ramag netic shif t, ppm -15 -10 -5 0 5 10 15

Correlation between the calculated and experimental

paramagnetic shifts in the 1_{H NMR spectrum of [Yb(CyMe}

4

-BTTP)(NO₃)₃]. 99 % intervals indicated by dotted lines.

Optimized Solution Structure

of Ytterbium mono-Complex

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Conclusions

• Low DAm values but good separation factors (SFAm/Eu) are

observed for CyMe

₄

-BTTP in 1-octanol.

• Higher DAm values obtained with 2-bromohexanoic acid at low

acidity.

• With lanthanide perchlorates, CyMe

₄

-BTTP forms highly-crowded

1:2 complexes - aliphatic rings conformationally immobile.

• With lanthanide nitrates, CyMe

₄

-BTTP forms less crowded 1:1

complexes – aliphatic rings conformationally mobile.

• Nitrate ions compete with the ligand for coordination sites on the

metal – less hydrophobic 1:1 complexes.

• Solution structure of 1:2 complex with Yb(ClO

₄

)

₃

determined –

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