810
O.P. Lam et al. / C. R. Chimie 13 (2010) 803–811
procedures. [16] The 4-hydroxydiamantane (99+%) was
obtained from Chevron Technology Ventures as a generous
gift and used as received. Thionyl chloride (> 99%) and
azidotrimethylsilane (95%) were purchased from Aldrich
and used as received. The 4-tert-butylphenol (97%) was
purchased from Acros Organics and also used as received.
4.8. Synthesis of [((DiaArO)3tacn)U(Cl)] (2)
Dichloromethane (7 L, 0.11 mmol) diluted in DME
m
(ꢃ2 mL) was added dropwise to a stirring solution of 1
(0.150 g, 0.11 mmol) in DME (ꢃ6 mL). Immediately the
red-brown reaction solution turned pale green. The
reaction was allowed to proceed at room temperature
for 5 hours. The reaction mixture was filtered and volatiles
were removed yielding 2 as pale green solids. Yield: 0.123 g
(0.085 mmol, 77%).
4.4. Synthesis of 4-chlorodiamantane
In a flask fitted with a reflux condenser, thionyl
chloride (18.0 mL, 0.0248 mol) was added to 4-hydro-
xydiamantane (5.00 g, 0.0245 mol. The mixture was
heated to reflux at 90 8C for 2 h. At room temperature,
the remaining thionyl chloride is removed in vacuo. The
residue is taken up in dichloromethane (50 mL) and
washed three times (50 mL) with distilled water. The
volatiles in the organic fraction were removed in vacuo to
yield a white powder. Yield: 5.24 g (0.0235 mol, 96%).
Elemental analysis (%) calcd: C, 75.49; H, 8.60. Measured:
C, 75.67; H, 8.65.
4.9. Synthesis of [((DiaArO)3tacn)U(NTMS)] (3)
Azidotrimethylsilane (14 mL, 0.11 mmol) diluted in
hexane (ꢃ2 mL) was added dropwise to a stirring solution
of 1 (0.150 g, 0.11 mmol) in DME (ꢃ6 mL). The reaction
solution turns dark brown-orange and evolution of
dinitrogen was observed. Stirring was continued for
4 hours. The reaction mixture was filtered and volatiles
were removed to obtain 3 as brown-orange solid. Yield:
0.121 g (0.081 mmol, 76%).
4.5. Synthesis of 2-diamantyl-4-tert-butylphenol
4.10. Crystallographic details for 2
In
a
flask equipped with
a
reflux condenser,
4-chlorodiamantane (5.00 g, 0.0224 mol) and 4-tert-butyl-
phenol (8.41 g, 0.056 mol) were heated to reflux at
140 8C. The melt was stirred for 12 hours. At room
temperature, the solid mass was placed on a Kugelrohr
device at 100 8C for 20 hours or until a pure white product
was obtained, checked by 1H-NMR. Yield: 5.88 g
(0.0175 mol, 78%). 1H-NMR (400 MHz, dichloromethane-
Green block crystals, grown from slow diffusion of
acetonitrile into a dichloromethane solution of 2 at room
temperature, were coated with isobutylene oil on a
microscope slide. A crystal of approximate dimensions
0.25 Â 0.21 Â 0.14 mm3 was selected and mounted on a
nylon loop. A total of 87361 reflections (–30 ꢄ h ꢄ 30,
–15 ꢄ k ꢄ 16, –32 ꢄ l ꢄ 32) were collected at T = 150(2) K in
d2, 20 8C)
d
= 7.27 (d, 1H), 7.07 (dd, 1H), 6.58 (d, 1H), 4.80 (s,
the
u
range from 3.29 to 25.688, of which 16647 were
(I)]
1H) 2.20 – 1.70 (m, 19H).
unique (Rint = 0.0726) and 13714 were observed [I > 2
s
on a Bruker-Nonius KappaCCD diffractometer using MoK
a
4.6. Synthesis of (DiaArOH)3tacn (L3)
radiation (
l
= 0.71073 A). The structure was solved by
˚
direct methods (SHELXTL NT 6.12, Bruker AXS, Inc., 2002).
All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were placed in calculated idealized
positions. One of the t-Bu groups is disordered, with two
refined alternative positions being occupied by 36(2) and
64(2)% for C54 – C56 and C54A – C56A, respectively. The
compound crystallizes with a number of solvent molecules
of which the positions of one acetonitrile and two
dichloromethane molecules were located. Apart from this
the crystal structure contains two solvent accessible voids
that are occupied by heavily disordered solvents. Here,
the Squeeze algorithm was applied [18]. The residual peak
In a flask fitted with a reflux condenser, triazacyclono-
nane (0.43 g, 3.3 mmol) and paraformaldehyde (0.30 g, 9.9
mmol) were heated to 80 8C in 1-propanol. After 2 hours,
the 2-diamantyl-4-tert-butylphenol (5.00 g, 14.9 mmol)
was added and the reaction mixture was allowed to stir at
80 8C for an additional 14 hours. During the cooling process
to room temperature, a white precipitate started to form. A
few drops of water were added to the reaction mixture to
facilitate complete precipitation of the product. The white
precipitate was collected by filtration and washed three
times (10 mL) with ethanol. Yield: 2.83 g (2.4 mmol, 72%).
1H-NMR (400 MHz, dichloromethane-d2, 20 8C)
d
= 7.19 (d,
and hole electron density were 3.293 and –3.787e.AÀ3. The
˚
3H), 6.79 (d, 3H), 3.70 (s, 6H), 2.77 (s, 12H), 2.22 – 1.68 (m,
57H), 1.27 (s, 27H).
absorption coefficient was 2.026 mmÀ1. The least-squares
refinement converged normally with residuals of
R1 = 0.1045, wR2 = 0.2070, and GOF = 1.241 (all data).
4.7. Synthesis of [((DiaArO)3tacn)U] (1)
C
85H115N4O3Cl5U, monoclinic, space group P21/c, a =
˚
24.996(5), b = 13.380(2), c = 27.038(3) A,
b = 101.300(9)8,
3
˚
A solution of [U(N(SiMe3)2)3] (0.643 g, 0.89 mmol) in
1,2-dimethoxyethane (ꢃ8 mL) was added dropwise to a
stirring solution of (DiaArOH)3tacn (L3) (1.00 g, 0.85 mmol)
in DME (ꢃ7 mL). Within 10 minutes, a red-brown solution
is observed. The reaction was allowed to stir for 4 hours.
The reaction mixture was filtered through Celite and the
volatiles were removed in vacuo to obtain 1 as a red-brown
powder. Yield: 0.823 g (0.70 mmol, 82%).
V = 8867(2) A , Z = 4,
r
calcd = 1.240 Mg/m3, F(000) = 3416,
R1(F) = 0.0910, wR2(F2) = 0.2014 [I > 2
s(I)]. CCDC reference
number: 763284.
4.11. Crystallographic details of 3
Brown plate crystals, grown from a saturated solution
of 3 in hexane at room temperature, were coated with