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F. Basuli et al. / Inorganica Chimica Acta 360 (2007) 246–254
CHMe2), 2.88 (septet, 1 H, CHMe2), 1.56 (s, 9 H, ArN-
(tBu)CCHC(tBu)) 1.46 (d, 6 H, CHMe2)s, 1.36 (d, 6 H,
CHMe2), 1.26 (d, 3 H, CHMe2), 1.25 (d, 3 H, CHMe2),
1.22 (m, 4 H, THF), 1.09 (d, 3 H, CHMe2), 1.06 (d, 3 H,
CHMe2), 1.04 (s, 9 H, ArN(tBu)CCHC(tBu)). 13C NMR
(23 ꢁC, 100.6 MHz, C6D6): d 258.9 (ArN(tBu)CCHC(tBu)),
193.3 (ArN(tBu)CCHC(tBu)), 158.3, 144.9, 144.7, 141.9,
141.4, 127.9, 126.6, 124.3, 123.6, 122.9, 122.3, 73.54
(THF), 43.53 (ArN(CMe3)CCHC(CMe3)), 43.24 (ArN-
(CMe3)CCHC(CMe3)), 31.01 (ArN(CMe3)CCHC(CMe3)),
30.14 (ArN(CMe3)CCHC(CMe3)), 28.65 (CHMe2), 28.09
(THF), 27.20 (CHMe2), 26.04 (CHMe2), 25.42 (Me),
24.91 (Me), 24.83 (Me), 24.70 (Me), 24.25 (Me), 23.22
(Me). Anal. Calc. for C39H61N2OClTi: C, 71.27; H, 9.35;
N, 4.26. Found: C, 71.54; H, 9.33; N, 4.56%.
(CHMe2), 29.06 (ArN(CMe3)CCHC(CMe3)), 28.79
(CHMe2), 28.51 (CHMe2), 27.73 (CHMe2), 25.78 (Me),
24.28 (Me), 23.86 (Me), 23.76 (Me), 23.69 (Me), 23.53
(Me). Anal. Calc. for C47H71N3Ti: C, 77.76; H, 9.86; N,
5.79. Found: C, 77.48; H, 9.79; N, 5.47%.
3.2.4. Synthesis of
[Li(Et2O)][(ArN(tBu)CCHC(tBu))Ti@NAr(Et2O)]
(4)
In
a vial was suspended (nacnac)TiCl2 (200 mg,
0.32 mmol) in pentane (10 mL) and the solution was cooled
to À35 ꢁC. To the solution was added a cold solution of
tBuLi (63.2 mg, 0.99 mmol) followed by 6 drops of Et2O.
The solution was allowed to stir for 2 h. The resulting solu-
tion was filtered, and the filtrate was concentrated and
cooled to À35 ꢁC to yield red crystals of [Li(Et2O)]-
3.2.2. Synthesis of (nacnac)Ti(NHAr)Cl (2)
a
[(ArN(tBu)CCHC(tBu))Ti@NAr(Et2O)]
(4)
(184 mg,
In
flask was dissolved (nacnac)TiCl2 (500 mg,
0.26 mmol, 81% yield). 1H NMR (23 ꢁC, 399.8 MHz,
C6D6): d 7.39–6.99 (m, 6 H, Ar-H), 6.88 (s, ArN
(tBu)CCHC(tBu)), 3.89 (septets, 1 H, CHMe2), 3.49–3.19
(m, 10 H, CHMe2, Et2O), 2.88 (septet, 1 H, CHMe2),
1.72 (s, 9 H, ArN(tBu)CCHC(tBu)), 1.58–1.54 (overlapping
doublets, 12 H, CHMe2), 1.35 (s, 9 H, ArN(tBu)-
CCHC(tBu)), 1.09–0.84 (24 H, Et2O and CHMe2). 13C
NMR (23 ꢁC, 100.6 MHz, C6D6): d 210.5 (ArN(tBu)-
CCHC(tBu)), 157.1 (ArN(tBu)CCHC(tBu)), 152.6 (C6H3),
142.3 (C6H3), 140.2 (C6H3), 139.5 (C6H3), 125.4 (C6H3),
123.9 (C6H3), 122.7 (C6H3), 116.9 (C6H3), 116.4 (C6H3),
102.6 (ArN(tBu)CCHC(tBu)), 66.17 (Et2O), 63.78 (Et2O),
42.32 (ArN(CMe3)CCHC(CMe3)), 39.30 (ArN(CMe3)-
CCHC(CMe3)), 33.21 (ArN(CMe3)CCHC(CMe3)), 32.76
(ArN(CMe3)CCHC(CMe3)), 28.57 (CHMe2), 26.64
(CHMe2), 26.47 (CHMe2), 25.45 (Me), 24.89 (Me), 24.76
(Me), 23.96 (Me), 13.94 (Et2O), 12.85 (Et2O). Anal. Calc.
for C43H73N2O2LiTi: C, 73.27; H, 10.44; N, 3.97. Found:
C, 73.11; H, 10.25; N, 4.25%.
0.80 mmol) in toluene and the solution was cooled to
À35 ꢁC. To the cold solution was added dropwise a cold
toluene (20 mL) solution containing Li(NHAr) (144.7 mg,
0.79 mmol). The solution was allowed to stir for 2 h, fil-
tered, and then dried in vacuo. The green residue was
extracted with Et2O and filtered. The resulting filtrate
was concentrated and cooled to À35 ꢁC to yield green crys-
tals of (nacnac)Ti(NHAr)Cl (2) (521 mg, 0.68 mmol, 85%
1
yield). H NMR (23 ꢁC, 399.8 MHz, C6D6): d 11.5 (Dm1/2
= 16 Hz), 5.73 (Dm1/2 = 32 Hz), 5.56 (Dm1/2 = 25 Hz), 5.41
(Dm1/2 = 24 Hz), 4.54 (Dm1/2 = 34 Hz), 3.69 (Dm1/2
57 Hz), 2.61 (Dm1/2 = 26 Hz), 1.70 (Dm1/2 = 30 Hz), 1.35
(Dm1/2 = 105 Hz). eff = 1.88 lB (C6D6, 298 K Evans’
=
l
method). Anal. Calc. for C47H71N3ClTi: C, 74.14; H,
9.40; N, 5.52. Found: C, 74.29; H, 8.92; N, 5.60%.
3.2.3. Synthesis of
(ArN(tBu)CCHC(tBu))Ti@NAr(NHAr) (3)
In a vial was dissolved 2 (193 mg, 0.25 mmol) in toluene
(10 mL) and the solution was cooled to À35 ꢁC. To the
solution was added a cold THF (5 mL) suspension contain-
ing KC8 (37.7 mg, 0.28 mmol). The solution was allowed to
stir for 20 min, filtered and then dried in vacuo. The red
residue was extracted with Et2O and filtered. The resulting
filtrate was concentrated and cooled to À35 ꢁC to yield red
crystals of (ArN(tBu)CCHC(tBu))Ti@NAr(NHAr) (3)
(162 mg, 0.22 mmol, 88% yield). 1H NMR (23 ꢁC,
399.8 MHz, C6D6): d 7.16–6.78 (m, 10 H, Ar-H, ArN
(tBu)CCHC(tBu)), 4.32 (br, 2 H, CHMe2), 3.65 (septet,
1 H, CHMe2), 3.21 (septet, 2 H, CHMe2), 2.88 (septet,
1 H, CHMe2), 1.29–1.12 (36 H, ArN(tBu)CCHC(tBu) and
CHMe2), 1.06–1.02 (12 H, ArN(tBu)CCHC(tBu) and
CHMe2), 1.00 (d, 6 H, CHMe2). The NH resonance was
3.3. Crystallographic details
Inert atmosphere techniques were used to place the crys-
tal onto the tip of a diameter glass capillary (0.1 mm) and
mounted on a SMART6000 (Bruker) at 119 K. A prelimin-
ary set of cell constants was calculated from reflections
obtained from three nearly orthogonal sets of 20–30
frames. Data collection were carried out using graphite
monochromated Mo Ka radiation with a frame time of
5–30 s with a detector distance of 5.0 cm. A randomly ori-
ented region of a sphere in reciprocal space was surveyed.
Three sections of 606 frames were collected with 0.30ꢁ steps
in x at different / settings with the detector set at À43ꢁ in
2h. Final cell constants were calculated from the xyz cent-
roids of strong reflections from the actual data collection
after integration (SAINT) [40]. The structure was solved
using SHELXS-97 and refined with SHELXL-97 [41]. A direct-
methods solution was calculated which provided most
non-hydrogen atoms from the E-map. Full-matrix least-
squares/difference Fourier cycles were performed which
1
not located in the H NMR spectrum. 13C NMR (23 ꢁC,
100.6 MHz, C6D6): d 250.4 (ArN(tBu)CCHC(tBu)), 188.6
(ArN(tBu)CCHC(tBu)), 159.6, 149.4, 140.8, 140.3, 140.1,
136.9, 124.8, 124.5, 122.9, 122.2, 123.0, 121.2, 120.9,
43.44 (ArN(CMe3)CCHC(CMe3)), 41.88 (ArN(CMe3)-
CCHC(CMe3)), 30.40 (ArN(CMe3)CCHC(CMe3)), 30.35