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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.
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
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
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
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
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
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