1

Cours de Chimie Séparative n °°°° 8:

Progrès Récent dans la Chimie Moléculaire des Actin ides

1 – Chimie Structurale

2 - Réactivité

2

Ln

Am CmNp BkU Cf EsPu

Orbitals 5f -> activdelocalised

High number oxidation sates (III, IV, V, VI, VII)

Light Actinides

Important Differences : Light Actinides / Lanthanides

Light Actinides / Heavy Actinides

Few Differences : Heavy Actinides / Lanthanides

Specificity: chemistry and physics of 5f electrons and o rbitals

Heavy Actinides

Orbitals 5f -> inactivLocalised

Few oxidation sates (II,III, IV)

Orbitals 4f -> inactivFew oxidation sates (II,III, IV)

Lanthanides

Solid Solution

3

Th IVPa IV VU III, IV, V, VINp III, IV, V, VI, VIIPu III, IV, V, VI, VII, (VIII)Am III, IV, V, VI, (VII)Cm III, IVBk, Cf… III

Stabilité des composés d’actinides

Advanced inorganic Chemistry, Cotton et Wilkinson, 5ed.

1.60.911.140.06MO22+/ MO2

+

1.740.45MO2+/ M3+

1.041.170.740.58MO2+/ M4+

1.691.030.68MO22+/ M3+

1.040.940.32MO22+/ M4+

3.12.30.980.15-0.63-3.7M4+/ M3+

-0.9-1.25-1.3-1.38-1.83M4+/ M

-2.32-2.03-1.79-1.8M3+/ M

CmAmPuNpUTh

« ordre de stabilité »

AnO 22+

U, Np, Pu, Am

An n+

n=3: Am, Pu, Np, U, ThN=4: Np, Pu, U, Am

Potentiel Redox Formel (V) 25°C, 1M HClO4

4

Table Actinide aqua ions – numbers of bound water molecules and metal–water distances

Ox state Th U Np Pu Am

6 MO22+ (2+n) 5.0 5.0 6.0

M–OH2 (A° ) 2.40 2.42 2.40–2.455 MO2

+ 5.0 4.0M–OH2 (A° ) 2.50 2.47

4 M4+ 10.0 9.0-10.0 11.2 8 or 9M–OH2 (A° ) 2.45 2.51-2.42 2.40 2.393 M3+ 9-10 9-10 10.2 10.3M–OH2 (A° ) 2.61 2.52 2.51 2.48

Lanthanide and Actinide Chemistry, Simon Cotton, Wiley 2006.

III, IV Pseudo spherical AnL n (n= 8-12)V, VI Bipyramide (O=An=O)L n Actinyl (2 + 3-6)VII … misc, poly oxo

Coordination des actinides

Série des actinyle 2+3 à 2+66

5

5-coordinate (2 + 3) 6-coordinate (2 + 4) 7-coordin ate (2 + 5) 8-coordinate (2 + 6)[UO2{N(SiMe3)2}3]

− Cs2[UO2Cl4] UO2Cl2 UO2F2(Me4N)2[UO2Br4] UO2(superphthalo) UO2CO3MgUO4 [UO2(NO3)2(Ph3PO)] [UO2(NO3)2(H2O)2]BaUO4 [UO2(L)5]

2+ CaUO4(L,H2O, DMSO, urea) SrUO4

Rb[UO2(NO3)3]

Haut degré d’oxydation (V et VI)

Lanthanide and Actinide Chemistry, Simon Cotton, Wiley 2006.

Coordination Exemples

Formula Thorium species present Coord. No.MTh(NO3)6 (M = Mg, Ca) [Th(NO3)6]2

− 12Ph4P+ [Th(NO3)5(OPMe3)2]

− [Th(NO3)5(OPMe3)2]− 12

Th(NO3)4.5H2O [Th(NO3)4(H2O)3] 11Th(NO3)4.2.67Me3PO {[Th(NO3)3(Me3PO)4]

+}2 [Th(NO3)6]2− 10, 12

Th(NO3)4.2Ph3PO [Th(NO3)4(OPPh3)2] 10Th(NO3)4.5Me3PO [Th(NO3)2(OPMe3)5]

2+ 9

Bas degré d’oxydation (III et IV)

Structure of Th(NO3)4(H2O)3.Structure of U(NO3)4(Ph3PO)2.

6

Un point concernant la chimie « structurale » récente

U

Np, Pu

7

U bas degré d’oxydation: Précurseurs

[U(OTf)3(MeCN)3]nNatrajan L. et al, Inorg. Chem., 2005, 44, 6115–6121

[UI3(THF)4]Berthet J.C. et al, Eur. J. Inorg.Chem., 1999, 2005

[UI4(PhCN)4]Enriquez A.E. et al, Inorg. Chem., 2005, 44, 7403

[UI4(MeCN)4] [UI2(MeCN)7][UI6] [UI4(py)3] [U(dmf)9]I4Berthet J.C. et al, Inorg. Chem., 2005, 44, 1142

8

U bas degré d’oxydation: Différence Ln(III) / U(III)

T. Mehdoui et al, Eur. J. Inorg. Chem. 2004, 19962000

U(III) U(IV) équilibre, donation d’un électron 5f/U dans les pi antiliantes de la pyrazine.

9

U différence U(III) Ce(III)

T. Mehdoui, J. C. Berthet, P. Thuery, L. Salmon, E. Riviere and M. Ephritikhine, Chem.–Eur. J., 2005, 11, 6994

[(Cp)2M(III)Terpy]+M=Ce et UDiff de D entre M-N est de 0.2A

Reaction avec Ph3SnH(donneur de radical H)

Uniquement avec U

[(Cp)2M(III)Terpy]+ Mieux décrit comme[(Cp)2U(IV)Terpy .- ]+

10

Composés U-Te moléculaire

[UI3(py)4] [Na(tmeda){N(TePiPr2)2}]

[LaI3(thf)4]

Table 1: Metal–tellurium bond lengths1 2 DeltaUTe(1) 3.1499(7) LaTe(1) 3.2074(9) 0.0575UTe(2) 3.1801(7) LaTe(2) 3.2437(10) 0.0636UTe(3) 3.1362(7) LaTe(3) 3.1893(10) 0.0531UTe(4) 3.1909(7) LaTe(4) 3.2559(12) 0.0650UTe(5) 3.1990(7) LaTe(5) 3.2614(11) 0.0624UTe(6) 3.1270(7) LaTe(6) 3.1875(10) 0.0605

Rayon de U(III) and La(III) are 1.04 Å and 1.045 Å différence 0.005 Å

Différence moyenne de Structure 0.060 Å

Effet Hard-Soft ? Covalence ? Transfert de charge

11

U bas degré d’oxydation: reaction N 2

G. N. Cloke and P. B. Hitchcock, J. Am. Chem. Soc., 2002, 124,9352.G. N. Cloke, J. C. Green and N. Kaltsoyannis, Organometallics,2004, 23, 832.

P. Roussel,W. Errington, N. Kaltsoyannis and P. Scott, J. Organomet. Chem., 2001, 635, 69.

N2

12

U bas degré d’oxydation: reaction CO

O. T. Summerscales, F. G. N. Cloke, P. B. Hitchcock, J. C. Green and N. Hazari, Science, 2006, 311, 829.

Calcul (DFT)

U(IV) 5f2

C3O32-

J.A.C.S, 2006, 128, 9602-9603

13

U reverse sandwich

U(I)(NRAr)3 + KC8 / toluene

(R =tBu, Ar=DiMethyl3,5-C6H3)

Electrons 1 à 4 les plus externes sont centrés sur U, non liant.

Electrons 5 à 8 sont 6d, 5f + LUMO du cycleSelon la localisation des electrons 5-8, le transfert de M vers le ligand on considérera U(II) oou U(IV)

P. Diaconescu, P. A. Arnold, T. A. Baker, D. J. Mindiola and C. C.Cummins, J. Am. Chem. Soc., 2000, 122, 6108

14

Arliguie T et al, J. Chem. Soc.,Dalton Trans., 1997, 2501.

[UI(NCtBuAr)3]KC8Naphtalene

Evans W. et al, Coord. Chem. Rev., 2006, 250, 911Evans et al, Chem. Comm., 2005. 4681.

U reverse sandwich

KC8C6H6

15

Composés U type cyclopentadienyl U(III)Cp 3

W. J. Evans, J. Organomet. Chem., 2002, 652, 61.W. J. Evans and B. L. Davis, Chem. Rev., 2002, 102, 2119.W. J. Evans, G. W. Nyce, K. J. Forrestal and J. W. Ziller, Organometallics, 2002, 21, 1050.W. J. Evans, S. A. Kozimor, G.W. Nyce and J.W. Ziller, J. Am. Chem. Soc., 2003, 125, 13831.W. J. Evans, S. A. Kozimor and J. W. Ziller, J. Am. Chem. Soc., 2003, 125, 14264.W. J. Evans, S. A. Kozimor and J. W. Ziller, Chem. Commun., 2005, 4681.W. J. Evans, G.W. Nyce and J.W. Ziller, Angew. Chem., Int. Ed., 2000, 39, 240.W. J. Evans, S. A. Kozimor, J. W. Ziller and N. Kaltsoyannis, J. Am. Chem. Soc., 2004, 126, 14533.

16

Composés U type cyclopentadienyl U(III)Cp

Cluster de ponts nitride and azide par reaction de NaN3 sur [U(C5Me4R)2][BPh4].

W. J. Evans, S. A. Kozimor and J. W. Ziller, Science, 2005, 309, 1835

17

Composés U cyclopentadienyl

U(III)U(IV)

T.J. Marks, Sciences 10 September 1982, Volume 217, Number 4564Evans W. et al, Coord. Chem. Rev., 2006, 250, 911

18

Composés U(IV) cyclopentadienyl

(C5Me5)2UI2

Acetonitrile

[(C5Me5)2U(NCMe)5]I2

(C5Me5)2UCl2

Jerome Maynadie et al, J. AM. CHEM. SOC. 2006 , 128, 1082-1083

Rôle du ligand X et du solvant

19

Composés U cyclopentadienyl

[Cp*2UI(py)]+ KCN + NR4CN

[Cp*2UI2]

U(III)U(IV)

Indépendant de X et du solvant

J. Mayndadié et al., Angew. Chem. Int. Ed. 2007, 46, 2010 –2012

U(III)U(IV)

+ CN-

U(IV)

trace O2

U(V)[Cp*2U(CN)5]-[NnBu4]3 [Cp*2U(CN)5]-[NnBu4]2

20

Composés U Uranocene

U et Th synthèse 1962Structure 1973 et 1993

1969

1981-83

1990-91

1995C7H7

2000

Cover Essay Organometallics 2004, 23, 3562-3583

J.C. Berthet et al, Organometallics, 27, No. 8, 2008

21

Composés Uranyle (V)

JC Berthet et al., Chem. Commun., 2006, 3184–3186J. Nocton et al., J. AM. CHEM. SOC. 2008, 130, 16633–16645

V VI

U=O 1,821 1,7632

U=O 1,817 1,7603

U-Oequ 2,427 2,2835

U-Oequ 2,455 2,2979

U-Oequ 2,439 2,3057

U-Oequ 2,431 2,3012

JC Berthet, Angew. Chem. Int. Ed. 2003, 42, 1952 – 1954

22J. Nocton et al., J. AM. CHEM. SOC. 2008, 130, 16633–16645

Composés Cation-cation Uranyle (V)

4

23

Composés Cation-cation Uranyle (V)

V. Mougel, Angew. Chem. Int. Ed. 2009, 48, 8477 –8480

L. Spencer et al, Inorganic Chemistry, Vol. 48, No. 24, 2009

P.L. Arnold et al., Coordination Chemistry Reviews 253 (2009) 1973–1978

24

Composés Uranyle (V)

Schettini et al., Inorganic Chemistry, Vol. 48, No. 24, 2009 David D. Schnaars et al, J. AM. CHEM. SOC. 2009, 131, 17532–17533

25

Composés Uranyle

P. Arnold et al., Nature 2008, Vol 451, 315.

26

Composés Uranyle

JC. Berthet et al., Radiochim. Acta 96, 189–197 (2008) JC Berthet et al., Inorg. Chem., Vol. 47, No. 15, 2008

UO2(OTf)2(Rbtp)

UO22+

UO2(NO3)2(MeCN)

UO2(OTf)2

[UO2(Mebtp)2][OTf]2

UO2(NO3)2(Mebtp)

27JC Berthet et al., Inorg. Chem., Vol. 47, No. 15, 2008

Composés Uranyle

UO2(OTf)2(Mebtp) [UO2(Mebtp)2][OTf]2 UO2(NO3)2(Mebtp)

28

UO2(NO3)2 UO2(NO3)2LL

L = Mebtp L = Prbtp

U

O3 O4

N2

N1 N6

O6

O7

O1

O2 U

N6

N1

N3O1

O2O7

O6 O3A

O4A

L = terpy

Michel Ephritikhine et al.

Composés Uranyle

29

Composés Pu

Low-Valent Molecular Plutonium Halide Complexes

Andrew J. Gaunt et al., Inorg; Chem., Vol. 47, No. 18, 2008

PuBr 3(thf) 4

[PuBr 2(H2O)6][Br]PuI3(thf) 4

30

[PuI2(thf) 4(py)][I 3]

[PuCl 2(thf) 5][PuCl 5(thf)]

Pu(III) cation Pu(IV) anion

Andrew J. Gaunt et al., Inorg; Chem., Vol. 47, No. 18, 2008

Composés Pu

Pu[N(SiMe 3)2]3Cl

Pu(III) Pu(IV)

31

Composés Pu

G.Andreev et al., Inorg. Chem. 2009, 48, 2343-2345

nucleotide

Pu L1 Ce L1

Géza Szigethy et al., Eur. J. Inorg. Chem. 2008, 2143–2147

32

Composés Pu

Decorporant

Pu

Ce

Anne E. V. Gorden, at al., Chem. Eur. J. 2005, 11, 2842 – 2848

33

Composés Pu-Np

I. A. Charushnikova et al., Radiochim. Acta 95, 495–499 (2007)

Structure de cation-cation de [AnO2(Bipy)(benzoate)]2 An = Np et Pu

Distance d, Å Distance d, ÅNp(1)–O(11) 1.796(4) Pu(1)–O(11) 1.760(10)Np(1)–O(12) 1.857(4) Pu(1)–O(12) 1.814(10)Np(1)–O(1) 2.434(4) Pu(1)–O(1) 2.417(10)Np(1)–O(2a) 2.419(4) Pu(1)–O(2a) 2.401(10)Np(1)–O(12a)2.479(4) Pu(1)–O(12a)2.488(9)Np(1)–N(1) 2.639(5) Pu(1)–N(1) 2.668(13)Np(1)–N(2) 2.627(5) Pu(1)–N(2) 2.646(12)

34

Composés Np(IV)

I. A. Charushnikova et al., Russian Journal of Coordination Chemistry, Vol. 29, No. 4, 2003, pp. 271–275

[Np(Urea) 8] SiW 12O40· 2Urea · H2O

Np(ClO4)4 + H4SiW12O40 + Urea

H(ClO4)

NpO2(ClO4) reduction cathode Hg

35

Composés Np(V)

Na[Np (V)O2(OH)2]

Philip M. Almond at al., Chem. Mater. 2007, 19, 280-285

Np(1)-OH(1) 2.437(3)Np(1)-OH(1)a 2.406(3)Np(1)-OH(2) 2.405(3)Np(1)-OH(2)b 2.377(3)Np(1)dO(3) 1.895(3)Np(1)-O(3)c 2.470(3)Np(1)dO(4) 1.879(3)

Np-Np super echange via un oxygène diagnétique(transition d’ordre ferromagnétique)

36Philip M. Almond et al., Inorg. Chem. 2004, 43, 958-963

Composés Np(V) – Np(IV)

Valence mixte connu dans les oxydes Np3O8 ou Np4O9

Np(NpO 2)2(SeO3)3 Synthèse hydrothermale NpO2, SeO2 CsCl dans H2O autoclave 180°C 3 jours

Environnement Np(IV)

Environnement Np(V)

Arrangement

37

[NpVIO2Cl2(thf)]n [{NpVIO2Cl2}{NpVO2Cl(thf)3}2]

Composés Np(VI) et Np(V) – Np(VI)

S. Cornet et al., Chem. Commun., 2009, 917–919

The NpVI–Oyl bond lengths in 2 are essentially the same (1.771(12) and 1.793(10) A ˚̊̊̊ ) and comparable with the analogous bond lengths in 1. As is typically the case for neptunyl(V) ‘cation–cation’ bonding, the NpV–Oyl oxygens coordinated to the NpVI centre are significantly longer (1.885(11) and 1.912(11) A ˚̊̊̊ ), and hence probably weaker, than the uncoordinatedNpV ‘yl’ oxygens (1.751(13) and 1.805(12)A ˚̊̊̊ ).The NpVI–ONp(V) bond lengths (2.317(11) and 2.303(11)A ˚ ) are significantly shorter than the Np–Othf bond length in 1 (2.396(11) A ˚ ) which suggests a stronger bonding interaction and at least partially explains why the axial oxygens of two {NpO2}+ moieties out-compete thf for coordination to neptunyl(VI) in 2.

38

[NpO 2(N3)(Phen)(H2O)]2· 3H2O

Composés Np(V)

N. A. Budantseva et al., Russian Journal of Coordination Chemistry, Vol. 29, No. 4, 2003, pp. 265–270

1/ NpO2(OH) + NaN3/Hydrazioc acide2/ + Phenanthroline H2O/Ethanol + HN3

Distance d, ÅNp(1)–O(1) 1.804(6) Np(1)–O(2) 1.826(6)Np(1)–N(1) 2.649(7)Np(1)–N(2) 2.613(7)Np(1)–N(3) 2.517(8) Np(1)–N(5) 2.492(9) Np(1)–O(3) 2.427(7) Np(2)–O(4) 1.846(6)Np(2)–O(5) 1.819(6)Np(2)–N(6) 2.609(7)Np(2)–N(7) 2.661(7)Np(2)–N(8) 2.555(8) Np(2)–N(10) 2.509(7)Np(2)–O(6) 2.423(6)

H bondContact Distance, ÅO(1)···O(7) 2.813(8)O(2)···O(8) 2.772(8) O(2)···O(8) 2.828(8) O(4)···O(3) 2.855(8) O(4)···O(6) 2.739(8) O(5)···O(9) 2.750(8) O(6)···O(7) 2.681(8) O(8)···O(7) 2.824(9) O(8)···O(9) 2.840(9) O(9)···O(3) 2.606(8)

39

Composés Pu (VII) et Np(VII)

Na4[NpO4(OH)2](OH) 2H2O, (I), and Na4[PuO4(OH)2](OH) 2H2O isostructuraux

Np1—O1 1.891 (2)Np1—O2 1.888 (2)Np1—O3 1.917 (2)Np1—O4 1.880 (2)Np1—O5 2.315 (2)Np1—O6 2.362 (2)

M Grigoriev et al., Acta Cryst. (2009). C65, i91–i93

40

Actinide expanded porphyrin

J.L. Sessler et al.,Coordination Chemistry Reviews 216–217 (2001) 411–434

U(IV) Th(IV)

41

Actinide expanded porphyrin

UO2(superphtalocyanine)

superphtalocyanine pentaphyrine

UO2(pentaphyrine)

42

alaskaphyrine

UO2(alaskaphyrine)

UO2(oxasapphyrine)

Pentaphyrine substituée

Actinide expanded porphyrin

43

UO2(alaskaphyrine dérivée)

Dérivée alaskaphyrine

Actinide expanded porphyrin

isoamethyrin

UO2(isoamethyrin)

44

Actinide expanded porphyrin

Cycle libre UO2(cycle)

J.L. Sessler et al., Inorganica Chimica Acta 341 (2002) 54/70

45

Actinide expanded porphyrin

46

Catalyse d’organo-actinides

- Oligomérisation d’alcynes

- Dimérisation d’alcynes

- Hydroamination d’alcyne

- Hydrosylilation d’oléfines

E. Barnea, M.S. Eisen, Coordination Chemistry Reviews 250 (2006) 855–899

47

Oligomerisation d’alcyne

48

Oligomerisation d’alcyne

Mécanisme possible

49

Hydroamination d’alcyne

50

Hydroamination d’alcyne

Possible mécanisme