Y.-M. Yao et al. / Polyhedron 22 (2003) 441Á
/446
445
1
as a white crystalline solid (9.7 g, 34%). H NMR (400
1.18 (d, 6H, CH(CH3)2), 1.24 (d, 6H, CH(CH3)2), 1.48
(m, 16H, THF), 1.65 (s, 3H, CH3), 1.78 (s, 3H, CH3),
3.22 (m, 2H, CH3CHCH3), 3.65 (m, 16H, THF), 4.88 (s,
MHz, CDCl3): 1.12 (d, 6H, CH3CHCH3), 1.21 (d, 6H,
CH3CHCH3), 1.68 (s, 3H, CH3), 2.01 (s, 3H, CH3),
2.97Á
/
3.04 (m, 2H, CH3CHCH3), 4.88 (s, 1H, CH Ä
/
1H, CH Ä
/
C(CH3)N), 6.69Á7.22 (d, 7H, aromatic pro-
/
C(CH3)N), 6.81 (d, 2H, aromatic protons), 7.13 (s,
3H, aromatic protons), 7.20 (d, 2H, aromatic proton),
12.54 (s, 1H, NH).
tons). IR (KBr, cmꢂ1): 3422(m), 2963(m), 2932(m),
2858(m), 1628(s), 1554(s), 1532(s), 1292(m), 1117(m),
1096(m), 1026(m), 926(w). Crystals suitable for X-ray
crystal structure studies were obtained by recrystalliza-
3.3. Synthesis of L1SmCl2(THF)2 (1)
tion from C6H5CH3 at ꢂ5 8C in a few days.
/
A solution of L1Li (25 ml, 5.26 mmol) in C6H5CH3/
C6H14 was slowly added to a suspension of SmCl3 (1.47
g, 5.73 mmol) in 40 ml THF at room temperature (r.t.).
The color of the solution gradually changed to yellow.
The reaction mixture was stirred overnight at r.t., then
centrifugation to remove the solution. Complex 1 was
3.6. Synthesis of L2YbCl2(THF)2 (4)
The synthesis of compound 4 was carried out as
described for 3, but anhydrous YbCl3 (1.83 g, 6.61
mmol) was used in place of SmCl3. The product was
collected in two crops by filtration (3.3 g, 67%), m.p.
obtained as a yellow powder (2.85 g, 81%), m.p. 182Á
/
179Á181 8C (dec.). Anal. Calc. for C31H44Cl3N2O2Yb:
/
184 8C (dec.). Anal. Calc. for C25H33Cl2N2O2Sm: C,
48.84; H, 5.41; N, 4.55; Sm, 24.46. Found: C, 48.27; H,
5.30; N, 4.58; Sm, 24.18%. IR (KBr, cmꢂ1): 3418(m),
2963(m), 2928(m), 2859(m), 1637(s), 1601(s), 1554(vs),
1532(vs), 1489(s), 1439(s), 1381(m), 1288(s), 1180(m),
1026(m), 752(m), 691(s). Crystals suitable for X-ray
crystal structure studies were obtained by recrystalliza-
C, 49.24; H, 5.87; N, 3.71; Yb, 22.89. Found: C, 48.64;
H, 5.91; N, 3.76; Yb, 22.64%. 1H NMR (400 MHz,
C6D6): 1.17 (d, 6H, CH(CH3)2), 1.24 (d, 6H,
CH(CH3)2), 1.59 (m, 16H, THF), 1.65 (s, 3H, CH3),
1.77 (s, 3H, CH3), 3.21 (m, 2H, CH3CHCH3), 3.90 (m,
16H, THF), 4.88 (s, 1H, CH Ä
/
C(CH3)N), 6.53Á7.41 (d,
/
7H, aromatic protons). IR (KBr, cmꢂ1): 3445(m),
2963(m), 2932(m), 2855(m), 1632(s), 1554(s), 1532(s),
1489(s), 1393(w), 1296(s), 1099(m), 1026(m), 926(w).
tion from THF at ꢂ5 8C in 2 days.
/
3.4. Synthesis of L1YbCl2(THF)2 (2)
3.7. X-ray structure determination
The synthesis of compound 2 was carried out as
described for 1, but anhydrous YbCl3 (1.28 g, 4.58
mmol) was used in place of SmCl3. The red precipitate
was obtained from THF solution at r.t. (2.48 g, 85%),
Suitable single crystals of complexes 1 and 3 were
each sealed in a thin-walled glass capillary, and intensity
data were collected on a Siemens SMART diffract-
ometer equipped with a CCD detector (for 1) or Siemens
m.p.
175Á
/
178 8C
(dec.).
Anal.
Calc.
for
C25H33Cl2N2O2Yb: C, 47.10; H, 5.18; N, 4.39; Yb,
27.16. Found: C, 46.43; H, 5.22; N, 4.26; Yb, 27.62%. IR
(KBr, cmꢂ1): 3422(m), 2974(s), 2927(m), 2859(m),
1620(s), 1556(vs), 1535(vs), 1489(s), 1439(s), 1373(w),
1364(s), 1300(s), 1038(m), 760(m), 694(s).
P4 diffractometer in v scan mode (for 3) using Mo Ka
˚
0.71073 A). Details of the intensity data
collection and crystal data are given in Table 3.
radiation (lꢀ
/
The crystal structures of these complexes were solved
by direct methods using the SHELXS-97 program and
expanded by Fourier techniques. All the non-hydrogen
atoms were refined anisotropically. Hydrogen atoms
3.5. Synthesis of L2SmCl2(THF)2 (3)
were all generated geometrically (CÃ
/
H bond lengths
A solution of n-BuLi in C6H14 (4.3 ml, 7.65 mmol)
was added to the THF (20 ml) solution of L2H (2.80 g,
7.61 mmol) at 0 8C, the mixture was stirred at 0 8C for 1
h, then another 2 h at r.t. The solution was then slowly
added to the suspension of SmCl3 (1.93 g, 7.53 mmol) in
60 ml THF at r.t. The color of the solution gradually
changed to yellow. The reaction mixture was stirred 48 h
at r.t. The solvent was removed in vacuum and
C6H5CH3 was added to extract the product. The
dissolved portion was removed by centrifugation. The
yellow micro crystals were obtained from the concen-
˚
fixed at 0.95 A) with assigned appropriate isotropic
thermal parameters.
4. Supplementary data
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC No. 177470 and 177471 for
complexes 1 and 3, respectively. Copies of this informa-
tion may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
trated C6H5CH3 solution at r.t. (3.6 g, 65%), m.p. 187Á
/
189 8C (dec.). Anal. Calc. for C31H44Cl3N2O2Sm: C,
50.77; H, 6.05; N, 3.82; Sm, 20.50. Found: C, 50.14; H,
1
6.00; N, 3.83; Sm, 20.75%. H NMR (400 MHz, C6D6):
(fax: ꢁ
/
44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk