Synthesis and characterization of new thorium and uranium phenolate complexes

Article abstract of DOI:10.1016/j.jorganchem.2006.10.071

The reaction between the chelating amino bisphenole ligand (ONOO)H₂ (1) [ONOO = MeOCH₂ CH₂ N {CH₂ - (2 - O - C₆ H₂ - Bu₂^t - 3, 5)}₂] and (ONNO)H₂

Full text of DOI:10.1016/j.jorganchem.2006.10.071

Journal of Organometallic Chemistry 692 (2007) 1074–1080
www.elsevier.com/locate/jorganchem
Synthesis and characterization of new thorium and uranium
phenolate complexes
a
a
a
a
b
Tamer Andrea , Eyal Barnea , Mark Botoshansky , Moshe Kapon , Elisheva Genizi ,
b
a,
*
Zeev Goldschmidt , Moris S. Eisen
a
The Schulich Faculty of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa 32000, Israel
b
Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Received 11 October 2006; accepted 26 October 2006
Available online 10 November 2006
Abstract
The reaction between the chelating amino bisphenole ligand (ONOO)H2 (1) ½ONOO ¼ MeOCH2CH2NfCH2-ð2-O-C6H2-But2-3; 5Þg2ꢀ
and (ONNO)H2 (2) ½ONNO ¼ Me2NCH2CH2NfCH2-ð2-O-C6H2-But2-3; 5Þg2ꢀ with an excess of NaH gives the corresponding bis-
sodium salts 3 and 4 quantitatively. The salts were reacted with thorium tetrachloride at room temperature to obtain the corresponding
(ONOO)ThCl2 (5) and (ONNO)ThCl2 (6) complexes. However, ThCl4 and UCl4 react with (3) at higher temperatures to give the cor-
responding isomorphous homoleptic complexes (ONOO)2Th (7) and (ONOO)2U (8). We have also synthesized and characterized a tho-
rium salicylaldiminato complex L3ThCl (11) ½L ¼ ðC6H5ÞNCHð2-O-C6H2-But2-3; 5Þꢀ, in order to study the effect of the bridged ligand on
the molecular structure.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Organoactinides; Phenolate complexes; Salicylaldiminato complexes; Homoleptic complexes
1. Introduction
modification allowed the formation of (ONXO)MR
(M = Yb, Er) [2] and (ONXO)MR2 (M = Ti, Zr, Hf, Ta)
complexes [3–5]. Interestingly, the latter complexes were
found to be highly active in various polymerization reac-
tions [4].
The use of the salicylaldiminato ligand (9) also has been
widely studied in the polymerization of terminal olefins [6].
It was found that the steric demand of the substituents on
the phenyl groups plays a major role in the catalytic activ-
ity of these complexes; namely, the bigger the R group, the
higher the activity [7].
During the last decade we have developed non-metallo-
cene group 4 complexes and study their utilization for
various catalytic processes [8,9]. In addition, we have
found that metallocene complexes of the actinides are
excellent catalysts for parallel demanding chemical trans-
formations with complementary reactivities [9]. Recently,
we have found that replacing the cyclopentadienyl moiety
of the organoactinide metallocenes by amido groups
introduced some unexpected reactivities [10,11]. Hence,
The substituted amino bisphenole compounds are well-
known easy to modify ligands, their salts are used as
dianionic precursors with early transition metals [1], late
transition metals [2] and lanthanides [2]. For group 4 met-
als, the first generation of these ligands (ONO) (X = CH3
in Scheme 1) mainly gave the non-reactive homoleptic
complexes L2M [3]. Two modifications were made in order
to prevent the metathesis of the second ligand: (i) increas-
ing the steric bulk of the substituents on the aryl group;
(ii) attaching a donating group to the side chain terminus
(X = O, N, S) to obtain the so called ‘‘second generation’’
ligands (ONXO); in order to induce the coordinative satu-
ration and to avoid the activation of the second ligand. The
first modification allowed the formation of (ONO)MR2
complexes (M = Ti, Zr, Hf, Ta) [2,3], whereas the second
*
Corresponding author.
E-mail address: chmoris@tx.technion.ac.il (M.S. Eisen).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.10.071

T. Andrea et al. / Journal of Organometallic Chemistry 692 (2007) 1074–1080
1075
Cl
Cl
X
tBu
tBu
Th
O
ThCl4
O
toluene, RT
N
tBu
t
Bu
(5) X = OMe
(6) X = NMe2
Na Na
tBu
tBu
tBu
tBu
OH HO
N
O
O
2NaH
THF, RT
+ 2H2
N
X
UCl4
toluene, RT
tBu
M
tBu
tBu
tBu
tBu
tBu
O
O
X
X
1/2
+ 1/2 MCl4
tBu
(1) X = OMe
(2) X = NMe2
(3) X = OMe
(4) X = NMe2
N
tBu
MCl4
2
toluene, 700C
(7) M = Th ; X = OMe
(8) M = U ; X = OMe
Scheme 1. Synthesis of (ONOO)ThCl2, (ONNO)ThCl2, (ONOO)2Th and (ONOO)2U complexes.
the introduction of new ancillary ligands in the synthesis
of organoactinide complexes is expected to pioneer new
catalytic processes.
Herein, we report the synthesis and structure of new
actinide complexes containing the amino bisphenolate
motifof the type (ONOO), and (ONNO) and the salicylal-
diminato ligand.
2. Results and discussion
The sodium salt 3 [12] was prepared from 1 [3a]. The
sodium salt was reacted with 1 equiv. of ThCl4 Æ 3THF in
toluene at room temperature to give complex 5 as a white
solid compound (Scheme 1). The complex was isolated,
recrystallized and characterized by elemental analysis and
NMR spectroscopy. Our attempts to obtain suitable single
crystals for X ray characterization at low temperatures
with a mixture of various solvents failed due to the rapid
formation of microcrystalline material. When the reaction
was performed at elevated temperature (70 ꢁC) (Scheme 1)
the homoleptic complex 7 was the main product obtained
as a white solid and characterized by elemental analysis,
NMR and X-ray diffraction (Fig. 1). The same complex
can be prepared by reacting one equivalent of the ligand salt
3 with complex 5 at 70 ꢁC in toluene. A similar procedure
was followed with UCl4, to obtain complex 8 regardless
of the ratio between the ligand and the metal. Complex 8
was isolated as a green solid and characterized by elemental
analysis, NMR and X-ray diffraction (Fig. 1). The forma-
tion of complex 8 as the main product indicates that for
uranium the introduction of the second ligand must be
much faster than the first one. Hence, it seems plausible that
the first ligand (ONOO) activates the intermediate complex
(ONOO)UCl2 towards complex 8.
Fig. 1. ORTEP view of (ONOO)2Th (7) and (ONOO)2U (8). (Ellipsoids
are presented at 50% probability.) Methyl groups of the Bu moiety were
omitted for clarity.
t
to a downfield shift. COSY, DEPT and HMQC spectra
showed that one proton at each benzylic moiety displays
agostic interaction with the metal center. This interaction
leads to a stereotopic discrimination between the two pro-
tons on the same benzylic carbon. The same stereotopic
feature was also observed in complex 7 having four differ-
ent chemical shifts for the benzylic protons (3.22 (2H), 3.24
(2H), 5.13 (2H), 5.72 (2H) ppm).
The X-ray structures of complexes 7 and 8 corroborate
our findings in solution. In both complexes the distance
between the metal and the four endo protons (referred to
1H NMR of complex 5 shows that the four benzylic pro-
tons split into two different sets of signals at different chem-
ical shifts (d 3.19 (2H) and 5.59 (2H) ppm). This NMR
behavior indicates that one set of benzylic protons are
interacting with the metal center more strongly, leading
˚
Ha at the bottom of Fig. 1) is between 3.17 A and
˚
3.78 A, whereas the distance between the metal and the
exo protons (referred to Hb at the bottom of Fig. 1) is

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T. Andrea et al. / Journal of Organometallic Chemistry 692 (2007) 1074–1080
Table 1
tive than the corresponding ether bond leaving an accessi-
ble vacant coordination site for future catalysis.
˚
Selected bond lengths (A) and angles (ꢁ) for (ONOO)2Th (7) and
(ONOO)2U (8)
In addition, we have studied the ‘‘cooperation effect’’
between the two bridged phenoxy groups by synthesizing
the thorium complex 11 (see Scheme 2). The complex was
prepared by the reaction between one equivalent of the sal-
icylaldiminato lithium salt [14] and ThCl4 Æ 3THF. The
final complex was characterized by NMR spectroscopy
and single crystal X-ray diffraction studies (Fig. 2).
Although the same metal–oxygen and metal–nitrogen
interactions are present in complexes 7 and 11, the earlier
complex is eight coordinative whereas the latter is seven
coordinative. The greater steric hindrance of the ligands
in complex 11 impedes to introduce the fourth ligand to
obtain the corresponding homoleptic complex. The single
chloride atom is fixed on the Z axis with a bond length
Complexes
7
8
M–O1
M–O2
M–O3
M–O4
M–O5
M–O6
M–N1
M–N2
2.262(4)
2.775(7)
2.256(4)
2.233(4)
2.624(4)
2.313(4)
2.765(5)
2.725(6)
2.232(11)
2.782(17)
2.202(11)
2.177(12)
2.590(14)
2.274(11)
2.707(13)
2.654(16)
O1–M–O4
O1–M–N1
O6–M–N2
O2–M–N1
102.53(18)
69.86(16)
71.75(17)
61.17(18)
101.65(4)
70.3(4)
73.2(4)
61.2(5)
N2–M–O1–O6
N2–M–O3–O4
70.5
71.4
69.6
72.1
˚
˚
of 2.68(1) A (compared to 2.79 A in [(OPhCH2-
PhO)2ThCl]+) [15]. The three nitrogen atoms are all located
in the same plane pointing towards the chloride atom, with
˚
˚
between 3.93 A and 4.39 A. Suitable crystals of complexes
7 and 8 were grown from concentrated toluene solutions.
Both molecular structures contain eight coordinated metal
centers. The closest coordination sphere around the metals
forms a tetrahedral geometry (created by the atoms O1,
O3, O4, O6 in both complexes). The pendant side arm in
the complexes coordinates to the thorium and uranium
with bond lengths of 2.70 A and 2.69 A, respectively,
unlike homoleptic lanthanide complexes where the side
arm is not coordinated to the metal center [13]. The resem-
blance between the molecular structure of complexes 7 and
8 (Table 1) in the solid state indicates that the 5f electrons
in complex 8 do not participate in the bonding, as expected
from inner orbitals.
˚
an average thorium–nitrogen bond length of 2.67(4) A
˚
˚
(compared to 2.74 A in (ONOO)2Th and 2.68 A in
(ONOO)2U). The three oxygen atoms are all located in
one plane driving the tert-butyl groups away from the chlo-
ride atom, the average metal–oxygen bond length is
2.22(3) A similar to 2.26 A in (ONOO)2Th and 2.22 A in
(ONOO)2U.
˚
˚
˚
˚
˚
In conclusion, we have successfully prepared and char-
acterized two dichloride thorium complexes (5 and 6) and
two homoleptic thorium (7) and uranium (8) complexes.
To understand the effect of the pendant arm donor (X)
on the molecular structure, we have prepared the thorium
complex of ligand 2 [5a] by reacting ThCl4 with the appro-
priate salt
4 at room temperature. The complex
(ONNO)ThCl2 (6) was obtained and isolated as a white
solid and characterized by NMR spectroscopy and elemen-
tal analysis. The high similarity between the NMR features
(multiplicity and chemical shifts) of complexes 5 and 6
allows us to propose structural resemblance between these
two complexes, and to conclude that the X motif do not
affect much the molecular structure of the actinide com-
plex. This result is indeed potentially important since we
might expect that a metal–amine bond would be more reac-
Fig. 2. ORTEP view of (L)3ThCl (11). (Ellipsoids are presented at 50%
probability.) Methyl groups of the Bu moiety were omitted for clarity.
t
MCl
nBuLi
Et2O
+ 3LiCl + 3THF
N
N
ThCl4 3THF
N
+ C4H10
OH
tBu
OLi
O
tBu
tBu
tBu
tBu
tBu
3
(9)
(10)
(11)
Scheme 2. Synthesis route for thorium salicylaldiminato complex (11).

T. Andrea et al. / Journal of Organometallic Chemistry 692 (2007) 1074–1080
1077
In addition, we have synthesized and characterized a tho-
rium salicylaldiminato complex, L3ThCl (11), in order to
study the effect of the bridging of the ligands on the molec-
ular structure of the complexes. The difference in structure
and ligation among the different complexes will entail us to
tailor new organic chemical transformations. Preliminary
results using these complexes show that they are better cat-
alyst for the coupling of terminal alkynes and isonitriles
[16]. A thorough study of these complexes in new catalytic
processes is underway and will be presented shortly (see
Table 2).
round bottom flask which was connected to a Schlenk-frit.
THF (30 ml) was syringed into the flask to dissolve the
ThCl4. The volume of the THF was reduced to 20 ml and
hexane (30 ml) was syringed carefully to form two layers.
The flask was cooled to ꢁ30 ꢁC and pale-yellow needle-like
crystals of ThCl4 Æ 3THF were formed. The crystals were
filtered, washed with hexane and dried in vacuum (14.9 g,
25.2 mmol, 81% yield).
Elemental analysis: calculated: C, 24.4; H, 4.1; Cl, 24.0.
Experimental: C, 25.5; H, 4.5; Cl, 22.9.
3.2.2. Synthesis of (ONOO)Na2 (3)
3. Experimental
A solution of ligand 1 (2 g, 3.90 mmol) in 10 ml THF
was added dropwise to a solution of NaH (0.37 g,
15.6 mmol) in 20 ml THF at ꢁ78 ꢁC under nitrogen atmo-
sphere over 10 min. the solution was then stirred at room
temperature for 2 h and filtered, the solid was washed three
times with cold THF. The filtrate was evaporated under
low pressure and a white fluffy solid was obtained (90%
yield).
1H NMR (300 MHz, THF-d8): d 6.98 (d, J = 2.4 Hz,
2H, Ar); 6.77 (d, J = 2.4 Hz, 2H, Ar); 4.10 (d,
J = 11.7 Hz, 2H, benzylic); 3.14 (t, J = 5.4 Hz, 2H, CH2);
2.87 (d, 11.7 Hz, 2H, benzylic); 2.66 (t, J = 5.4 Hz, 2H,
CH2); 2.41 (s, 3H, OCH3); 1.43 (s, 18H), (C(CH3)), 1.21
(s, 18H), (C(CH3)). d 13C NMR (125 MHz, THF-d8): d
168.0, 136.0, 129.0, 126.5 (ArC); 125.7, 122.0 (CH); 70.2,
65.4 (CH2); 56.8 (OCH3); 55.1 (CH2); 35.4, 33.6
(C(CH3)3); 32.0, 29.8 (C(CH3)3).
3.1. Instrumentation
All manipulations were performed on a high vacuum
(10ꢁ5 torr) line, or in a nitrogen filled vacuum atmospheres
glovebox with a medium capacity recirculator (1–2 ppm
O2). Argon and nitrogen were purified by passage through
˚
a MnO oxygen-removal column and a Davison 4 A molec-
ular sieve column. CCl4 was distilled from P2O5, all other
hydrocarbon solvents, toluene-d8 and THF-d8 (Cambridge
Isotopes) were distilled under nitrogen from Na/K alloy.
NMR spectra were recorded on Avance 500 or 300 spec-
trometer. Chemical shifts for 1H NMR and 13C NMR are
referenced to internal solvent resonances and are reported
relative to tetramethylsilane.
3.2. Syntheses
3.2.3. Synthesis of (ONNO)Na2 (4)
3.2.1. Synthesis of ThCl4 Æ 3THF
This compound was prepared from the precursor 2 by
identical procedure to that employed for compound 3. A
white fluffy solid was obtained (94% yield).
ThO2 (8.2 g, 31 mol) was placed in the center of a quartz
tube and heated overnight at 200 ꢁC under constant Ar
flush. A Schlenk-flask containing freshly distilled CCl4
was attached to the system. The temperature was raised
to 830 ꢁC and a slow Ar flow was directed through the
CCl4 to the quartz tube for 70 h. ThCl4 accumulated in
the cool part of the quartz tube. The reaction was moni-
tored by the consumption of the ThO2. After the comple-
tion of the reaction, the tube was transferred into the
glove box, and the white solids carefully transferred to a
1H NMR (300 MHz, THF-d8): d 7.01 (d, J = 2.7 Hz,
2H, Ar); 6.79 (d, J = 2.7 Hz, 2H, Ar); 4.08 (d, J = 11 Hz,
2H, benzylic); 2.89 (d, 11 Hz, 2H, benzylic); 2.58 (t,
J = 4 Hz, 2H, CH2); 1.91 (t, J = 4 Hz, 2H, CH2); 1.50 (s,
6H, N(CH3)2); 1.45 (s, 18H), (C(CH3)), 1.22 (s, 18H),
(C(CH3)).13C NMR (125 MHz, THF-d8): d 180.3, 136.0,
124.0, 122.5 (ArC); 121.8, 120.2 (CH); 66.3, 65.0, 63.2
(CH2); 55.6 (NCH3); 38.8, 37.5 (C(CH3)3); 28.5, 27.7
(C(CH3)3).
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for L3ThCl (11)
3.2.4. Synthesis of (ONOO)ThCl2 (5)
A mixture of ThCl4 Æ 3THF (0.22 g, 0.36 mmol) and the
di-sodium salt of ligand 3 (0.19 g, 0.35 mmol) were dis-
solved in 30 ml toluene and stirred at room temperature
over night under nitrogen atmosphere. A white precipitate
was formed and collected over a sinter glass. The collected
solid was dissolved in THF, filtered and washed with cold
THF three times. The filtrate was removed under reduced
pressure to produce (ONOO)ThCl2 (50% yield). The prod-
uct was crystallized from toluene/hexane at ꢁ30 ꢁC.
1H NMR (300 MHz, THF-d8): d 7.27 (d, J = 2.5 Hz,
2H, Ar); 6.99 (d, 2.5 Hz, 2H, Ar); 5.59 (br, 2H, benzylic);
3.57 (s, 3H, OCH3); 3.19 (br, 6H, benzylic); 2.67 (br, 2H,
Th–O1
Th–O3
Th–O5
Th–N2
Th–N4
Th–N6
Th–Cl1
2.205
2.234
2.239
2.661
2.667
2.702
2.689
O1–Th–N2
O3–Th–N4
O5–Th–N6
O1–Th–Cl1
O3–Th–Cl1
O5–Th–Cl1
68.81
67.72
67.43
114.66
124.69
130.33

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T. Andrea et al. / Journal of Organometallic Chemistry 692 (2007) 1074–1080
CH2); 1.45 (s, 18H), (C(CH3)), 1.29 (s, 18H), (C(CH3)).13C
NMR (125 MHz, THF-d8): d 162.1; 141.0, 136.8, 128.2
(ArC); 127.4, 125.0 (ArCH); 76.3, 66.5 (CH2); 65.6
(OCH3); 54.7 (CH2); 36.4, 35.5 (C(CH3)3); 33.0; 31.6
(C(CH3)3). Elemental analysis: calculated: C, 48.77; H,
6.33; N, 1.72; Cl, 8.72. Experimental: C, 49.00; H, 6.57;
N, 1.60; Cl, 9.00.
sure and a green solid was obtained (50% yield). The com-
plex was crystallized from toluene at ꢁ30 ꢁC.
1H NMR (300 MHz, Toluene d8): d 17.5 (br); 12.5 (br);
9.3 (br); 3.41 (s, 2H); 1.28 (s, 18H); ꢁ0.20 (s, 18H); ꢁ1.25
(s, 2H); ꢁ15.1 (br). Elemental analysis: calculated: C,
63.04; H, 8.18; N, 2.23. Experimental: C, 63.58; H, 8.11;
N, 2.00.
3.2.5. Synthesis of (ONNO)ThCl2 (6)
3.2.8. Synthesis of L3ThCl (11)
This complex was prepared from the sodium salt of
ligand 4 by identical procedure to that employed for com-
plex 5. A white solid was obtained (47% yield).
1.6 M nBuLi in hexane (2 ml, 3.20 mmol) was added
dropwise over 5 min to a diethylether solution of (3,5-di-
tert-butylsalicylidene)-aniline (9) (1 g, 3.20 mmol) in 20 ml
diethylether at ꢁ78 ꢁC under argon flow. The mixture
was allowed to warm to room temperature and stirred
for 12 h. the product was filtered and washed with diethy-
lether over a sinter glass. The filtrate was evaporated under
reduced pressure to produce the lithium salt (10) as yellow
powder (90% yield).
1H NMR (300 MHz, THF-d8): d 7.28 (d, J = 2.4 Hz,
2H, Ar); 6.97 (d, J = 2.4 Hz, 2H, Ar); 5.38 (br, 2H, ben-
zylic); 3.58 (br, 2H, benzylic); 3.22 (br, 2H, CH2); 2.63
(br, 2H, CH2); 2.26 (s, 6H, N(CH3)2); 1.46 (s, 18H),
(C(CH3)), 1.27 (s, 18H), (C(CH3)). 13C NMR (125 MHz,
THF-d8): d 163.3; 141.0; 131.8; 128.2 (ArC); 127.4, 125.1
(ArCH); 72.4, 69.0, 66.5 (CH2); 65.6 (NCH3); 36.4; 35.5
(C(CH3)3); 32.9; 31.6 (C(CH3)3). Elemental analysis: calcu-
lated: C, 49.45; H, 6.59; N, 3.39; Cl, 8.59. Experimental: C,
49.51; H, 6.79; N, 3.19; Cl, 8.07.
A solution of the lithium salt (0.25 g, 0.79 mmol) in
20 ml diethylether, was added dropwise over 20 min to a
solution of ThCl4 Æ 3THF (0.238 g, 0.40 mmol) in 20 ml
diethylether at ꢁ78 ꢁC. The mixture was allowed to warm
to room temperature and stirred over night. The mixture
was filtered and washed with diethylether. The filtrate
was evaporated under reduced pressure to obtain a brown
yellow solid. The crude product was dissolved with toluene
and filtered, the toluene filtrate was then removed by
reduced pressure and replaced with hexane, the solids
obtained were washed three times with hexane over a sinter
glass to obtain (Lig)3ThCl as bright yellow solid (50%
yield). The complex was crystallized from toluene/hexane
at ꢁ30 ꢁC.
3.2.6. Synthesis of (ONOO)2Th (7)
ThCl4 (0.27 g, 0.45 mmol) and di-sodium salt of ligand 3
(0.25 g, 0.45 mmol) were mixed together in 30 ml toluene
and heated to 70 ꢁC over night. A white precipitate was
formed and collected over a sinter glass. The solid was then
dissolved with THF and allowed to stand for 2 h till a white
solid was precipitated again. The solution was filtered and
the solid washed with cold THF three times. The filtrate
was then evaporated under reduced pressure and a white
solid was obtained (50% yield). The product was crystal-
lized from toluene/hexane at ꢁ30 ꢁC.
1H NMR (300 MHz, C6D6): d 8.23 (s, 1H, imine); 7.05–
6.79 (m, 7H, Ar); 1.35 (s, 9H, C(CH3)3); 1.25 (s, 9H,
C(CH3)3). 13C NMR (125 MHz, C6D6): d 171.7 (Imine
CH); 163.7, 155.4, 141.4, 140.5, 130.3 (ArC); 128.8, 127.9,
125.6, 122.2, 124.1(ArCH); 36.8, 35.9 (C(CH3)3); 31.3,
22.6 (C(CH3)3). Elemental analysis: calculated: C, 63.28;
H, 6.83; Cl, 2.96; N, 3.51. Experimental: C, 63.76; H,
6.52; Cl, 2.84; N, 3.35.
1H NMR (300 MHz, THF-d8): 7.24 (m, 4H, Ar); 7.04
(d, J = 2.4 Hz, 2H, Ar); 6.97 (d, J = 2.4 Hz); 5.72 (d,
J = 13 Hz, 2H, benzylic); 5.13 (d, J = 13 Hz, 2H, benzylic);
3.24 (d, J = 13 Hz, 2H, benzylic); 3.22 (d, J = 13 Hz, 2H,
benzylic); 3.14 (s, 6H, CH3); 2.95 (t, J = 4 Hz, 2H, CH2);
2.91 (t, J = 4 Hz, 2H, CH2); 2.44 (t, J = 3 Hz, 2H, CH2);
2.39 (t, J = 3 Hz, 2H, CH2); 1.42 (s, 18H), (C(CH3)), 1.34
(s, 18H), (C(CH3)); 1.22 (s, 18H), (C(CH3)); 1.18 (s,
18H), (C(CH3)). 13C NMR (125 MHz, THF-d8): d 163.2,
162.7, 138.9, 138.8, 136.2, 136.1, 128.9, 127.8 (ArC);
127.1, 126.7, 124.8, 124.4 (ArCH); 74.5, 65.9, 64.7 (CH2);
61.8 (OCH3); 49.7 (CH2); 35.8, 35.7, 34.6, 34.5
(C(CH3)3), 32.2, 32.1, 31.2, 31.1 (C(CH3)3) Elemental anal-
ysis: calculated: C, 63.34; H, 8.21; N, 2.24. Experimental:
C, 63.88; H, 7.91; N, 2.03.
3.3. X-ray crystallography
Crystal structure determination: Single crystal immersed
in Parathone-N oil was quickly fished with a glass rod and
mounted on the KappaCCD diffractometer under a cold
stream of nitrogen at 230 K. Data collection was carried
out with monochromatized Mo Ka radiation using x and
p scans to cover the Ewald sphere. Accurate cell parame-
ters were obtained with complete collections of intensities
and these were corrected in the usual way. The structure
was solved by direct methods and completed using succes-
sive Fourier difference maps. Refinement was performed
anisotropically with respect to the nonhydrogen atoms.
Hydrogens were placed at calculated positions and refined
using the riding model until convergence was reached (see
Table 3).
3.2.7. Synthesis of (ONOO)2U (8)
UCl4 (0.14 g, 0.36 mmol) and di-sodium salt of ligand 3
(0.19 g, 0.35 mmol) were mixed together in 30 ml dry tolu-
ene and heated to 70 ꢁC over night. The solution was dark
green above brown precipitate. The precipitate was col-
lected over a sinter glass and washed with cold toluene
three times. The filtrate was removed under reduced pres-

T. Andrea et al. / Journal of Organometallic Chemistry 692 (2007) 1074–1080
1079
Table 3
Crystallographic data for complexes 7, 8 and 11
Compound
7
8
11
Empirical formula
Formula weight
Crystal system
Space group
T (K)
C66H102N2O6Th
1251.54
Monoclinic
Cc
C66H102N2O6U
1257.53
Monoclinic
Cc
C63H78ClN3O3Th
1192.77
Monoclinic
P21/C
293(2)
0.71073
21.683(4)
13.083(3)
24.143(5)
90
119.63(3)
90
230.0(1)
0.71073
23.8940(3)
17.8770(4)
19.0820(3)
90
127.43
90
6472.10(19)
4
1.284
293(2)
0.71073
˚
Wavelength (A)
˚
a (A)
23.729(5)
17.855(4)
18.984(4)
90
126.97(3)
90
6426(2)
4
1.300
2.574
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
5953(2)
4
1.331
2.594
Z
Dcalc (Mgmꢁ3
)
Absorption coefficient (mmꢁ1
F(000)
)
2.352
2600
2608
2432
Crystal size (mm)
h Range for collection (ꢁ)
Reflections collected
Unique reflections
Rint
0.24 · 0.21 · 0.12
1.57–27.49
12199
12198
0.0254
0.15 · 0.08 · 0.04
1.57–25.35
23711
5785
0.1823
0.35 · 0.22 · 0.18
1.83–25.34
46043
10635
0.0820
Data/restrains/parameter ratio
All R indices
12198/2/0.6022
R1 = 0.0628
wR2 = 0.0822
R1 = 0.0392
wR2 = 0.0785
0.558 and ꢁ0.738
5785/17/347
R1 = 0.1115
wR2 = 0.1258
R1 = 0.0593
wR2 = 0.1117
1.126 and ꢁ1.362
10635/0/60
R1 = 0.0642
wR2 = 0.0760
R1 = 0.0349
wR2 = 0.0696
0.658 and ꢁ0.459
Final R indices [I > 2r(I)]
ꢁ3
˚
Largest difference in peak and hole (e A
)
[3] (a) E.Y. Tshuva, I. Goldberg, M. Kol, Z. Goldschmidt, Inorg. Chem.
40 (2001) 4263;
Acknowledgment
(b) E.Y. Tshuva, S. Groysman, I. Goldberg, M. Kol, Z. Goldschmidt,
Organometallics (2002) 662;
(c) E.Y. Tshuva, I. Goldberg, M. Kol, H. Weitman, Z. Goldschmidt,
Chem. Commun. (2000) 379.
This research was supported by the Israel Science Foun-
dation Administrated by the Israel Academy of Science
and Humanities under contract 1069/05.
[4] (a) S. Groysman, I. Goldberg, M. Kol, E. Genizi, Z. Goldschmidt,
Organometallics 23 (2004) 1880;
Appendix A. Supplementary material
(b) S. Groysman, S. Segal, I. Goldberg, M. Kol, Z. Goldschmidt,
Inorg. Chem. Commun. 7 (2004) 1889.
CCDC 628840, 628844 and 628845 contain the supple-
mentary crystallographic data for 7, 8 and 11. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.10.071.
[5] (a) E.Y. Tshuva, I. Goldberg, M. Kol, Z. Goldschmidt, Organomet-
allics 20 (2001) 3017;
(b) E.Y. Tshuva, I. Goldberg, M. Kol, Z. Goldschmidt, Chem.
Commun. (2001) 2120.
[6] (a) R. Furuyama, M. Mitani, J.-I. Morhi, R. Mori, H. Tanaka, T.
Fujita, Macromolecules 38 (2005) 1546;
(b) H. Makio, T. Fujita, Bull. Chem. Soc. Jpn. 78 (2005) 52.
[7] P.G. Cozzi, E. Gallo, C. Floriani, A. Chiesivilla, C. Rizzoli,
Organometallics 14 (1995) 4994.
[8] (a) For recent examples of activity of group-4 complexes in
polymerization see: V. Volkis, B. Tumanskii, M.S. Eisen, Organo-
metallics 25 (2006) 2722;
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