3170
T. Cai et al. / Journal of Organometallic Chemistry 694 (2009) 3167–3171
Table 4
[12]. Infrared spectra were recorded on a Magna-IR 550 spectrom-
eter as KBr pellet. 1H and 13C NMR spectra were recorded on a
Unity Inova-400. Melting points were measured in a sealed
Ar-filled capillary tube, and uncorrected. Lanthanide analyses were
carried out by a complexometric titration. Carbon, hydrogen and
nitrogen analyses were preformed by direct combustion on a Car-
lo–Erba EA 1110 instrument.
Details of the crystallographic data and refinements for complexes I, II and III.
I
II
III
Empirical formula
Formula weight
T (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C24H32NOYb
523.55
223(2)
0.71075
Monoclinic
P21
8.272(6)
14.583(9)
9.196(6)
90.00
C28H40NOYb
579.65
223(2)
0.71075
Orthorhombic
P212121
20.652(3)
12.177(2)
10.4921(18)
90.00
C24H32NOY
439.42
293(2)
0.71070
Monoclinic
P21
8.321(3)
14.686(4)
9.308(3)
90.00
4.2. Synthesis of complex I
b (Å)
c (Å)
A
THF solution (5 mL) of NaNH(2,6-Me2C6H3) (0.46 g,
a
(°)
3.20 mmol) was added to a stirring toluene solution (20 mL) of
(CH3C5H4)2YbCl(THF) (1.39 g, 3.20 mmol). The reaction mixture
was stirred for 12 h at room temperature. The volatiles were re-
moved under reduced pressure and the residue was extracted with
diethyl ether and the extracts were concentrated to about 10 mL.
Cooling the solution at 0 °C afforded the green crystals. Yield:
0.98 g (59%). Mp: 123–125 °C. Anal. Calc. for C24H32NOYb: C,
55.01; H, 7.12; N, 2.67; Yb, 32.14. Found: C, 54.74; H, 6.87; N,
2.82; Yb, 31.86%. IR (KBr, cmÀ1): 3467 (s), 2966 (w), 2922 (w),
2854 (w), 1623 (m), 1476 (s), 1378 (w), 1229 (vs), 1154 (vs),
1090 (w), 759 (m), 639 (m), 555 (m), 502 (s).
b (°)
97.645(15)
90.00
1099.3(13)
2
1.582
4.266
90.00
90.00
2638.5(8)
4
1.459
98.262(6)
90.00
1125.6(6)
2
1.296
2.603
c
(°)
V (Å3)
Z
Dcalc (g/cmÀ3
)
l
(mmÀ1
)
3.562
1172
F(0 0 0)
Crystal size (mm)
h Range
Reflections
collected
Independent
reflections
Parameters refined
Good-of-fit (GOF)
R
522
460
0.22 Â 0.16 Â 0.08 0.70 Â 0.30 Â 0.25 0.80 Â 0.52 Â 0.50
3.11–25.50
5394
3.23–27.48
9909
3.07–25.35
11 003
3462
5853
4077
211
292
253
0.973
0.0331
0.0605
0.980
0.0323
0.0504
0.933
0.0337
0.0571
4.3. Synthesis of complex II
wR
This complex was prepared as green crystals from the reaction
of (CH3C5H4)2YbCl(THF) (1.96 g, 4.51 mmol) with NaN-
H(2,6-iPr2C6H3) (0.90 g, 4.51 mmol) in THF (20 mL) under being
stirred for 12 h at room temperature and recrystallization from a
diethyl ether solution by a procedure similar to that used for the
synthesis of complex I. Yield: 1.21 g (46%). Mp: 160–163 °C. Anal.
Calc. for C28H40NOYb: C, 57.96; H, 6.90; N, 2.42; Yb, 29.96. Found:
C, 57.49; H, 7.12; N, 2.30; Yb, 29.40%. IR (KBr, cmÀ1): 3482 (s), 3068
(w), 2962 (vs), 2870 (w), 2773 (w), 1620 (s), 1438 (s), 1383 (m),
1213 (s), 1155 (vs), 1085 (w), 745 (s).
thermal parameters, and allowed to ride on their parent carbon
atoms. All the H atoms were held stationary and included in the
structure factor calculation in the final stage of full-matrix least-
squares refinement. The structures were solved and refined using
SHELEXL-97 program.
4.6. General procedure of addition of amines to nitriles
4.4. Synthesis of complex III
Amine (2 mmol) was added to a mixture of nitrile (1 mmol) and
catalyst (5 mol%). The reaction mixture was stirred at 100 °C for
24 h. The product was isolated by distilling the reaction mixture
under vacuum to remove unreacted starting materials. The residue
was recrystallized from toluene/hexane to afford the desired prod-
ucts. All products were identified by comparison with those of
authentic samples.
This complex was prepared as colorless crystals from the reac-
tion of (CH3C5H4)2YCl(THF) (1.47 g, 4.20 mmol) with NaNH(2,6-
Me2C6H3) (0.60 g, 4.20 mmol) in THF (20 mL) under being stirred
for 12 h at room temperature and recrystallization from a diethyl
ether solution by a procedure similar to that used for the synthe-
sis of complex I. Yield: 0.77 g (42%). Mp: 164–167 °C. Anal. Calc.
for C24H32NOY: C, 65.60; H, 7.28; N, 3.18; Y, 20.25. Found: C,
64.94; H, 7.01; N, 3.05; Y, 19.83%. IR (KBr, cmÀ1): 3467 (s),
2966 (w), 2922 (w), 2854 (w), 1623 (m), 1476 (s), 1378 (w),
1229 (vs), 1154 (vs), 1090 (w), 759 (m), 639 (m), 555 (m). 502
(s). 1H NMR(C6D6, 400 MHz, 25 °C): d 6.82–7.12 (m, 3H, Ph),
5.97–6.20 (m, 8H, MeC5H4), 4.46 (s, 1H, NH), 3.34 (s, 4H, THF),
2.24 (s, 6H, MeC5H4), 2.04 (s, 3H, CH3), 1.84 (s, 3H, CH3), 1.11
(s, 4H, THF).
Acknowledgements
Financial support from the National Natural Science Foundation
of China (20632040), the Major Basic Research Project of the Nat-
ural Science Foundation of the Jiangsu Higher Education Institu-
tions (07KJA15014) and PhD foundation of the Department of
Chinese Education is gratefully acknowledged.
Appendix A. Supplementary material
4.5. X-ray crystallography of complexes I–III
CCDC 721341, 721342 and 721343 contain the supplementary
crystallographic data for complexes I, II and III. These data can
be obtained free of charge from The Cambridge Crystallographic
tary data associated with this article can be found, in the online
Crystals of complexes I–III suitable for X-ray diffraction study
were sealed in a thin-walled glass capillary filled under argon. Dif-
fraction data were collected on a Rigaku Mercury CCD area detec-
tor in
x scan mode using Mo Ka radiation (k = 0.71070 Å). The
diffracted intensities were corrected for Lorentz polarization ef-
fects and empirical absorption corrections. Details of the intensity
data collection and crystal data are given in Table 4.
The structures were solved by direct methods and refined by
full-matrix least-squares procedures based on |F|2. All the non-
hydrogen atoms were refined anisotropically. The hydrogen atoms
were all generated geometrically, assigned appropriate isotropic
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