148
Y. Luo et al. / Journal of Organometallic Chemistry 662 (2002) 144ꢁ149
/
4.4. Synthesis of [CyNC(Ph)NCy]3Nd×
/
2THF (4)
tion reaction is given below (entry 1, Table 4). A 50 ml
Schlenk flask equipped with a magnetic stir bar was
charged with a 4.5 mM solution of initiator in toluene.
To this solution was added 1 ml of o-caprolactone using
rubber septum and syringe. The contents of the flask
were then vigorous stirred for 15 min at 25 8C. The
magnetic stirring was ceased within a few minutes due to
the viscosity. The reaction mixture was quenched by the
addition of 1 M HCl solution and then poured into a
cold petroleum ether to precipitate the polymer, which
was dried under vacuum and weighed.
A Schlenk flask was charged with N,N?-dicyclohex-
ylcarbodiimide (3.42 g, 16.58 mmol), THF (30 ml), and
a stir bar. To this solution was added PhLi (11.4 ml,
16.58 mmol, 1.45 M in Et2O) dropwise via syringe at
ambient temperature. The solution was stirred for 30
min and then added slowly to a pale-gray slurry of
NdCl3 (1.35 g, 5.39 mmol) in THF (60 ml). The color of
the solution immediately changed to blueꢁpurple. The
/
resulting solution was then stirred for 8 h and removed
the solvent in vacuo. The residue was extracted with
toluene and LiCl was removed by centrifugation. After
4.8. X-ray structural determination of 3 and 6
the extracts were concentrated and cooled to ꢃ
/
20 8C for
a day, blueꢁpurple crystals formed. Yield: 4.4 g (82%).
/
A suitable crystal was mounted in a thin-walled glass
capillary for X-ray structural analysis. Diffraction data
were collected on a Bruker SMART CCD area detector
using phi and omega scans. The structures were solved
by direct methods and refined by full-matrix least-
squares procedures based on ½F½2. All non-hydrogen
atoms were refined with anisotropic displacement coef-
ficients. Hydrogen atoms were treated as idealized
contributions. The structures were solved and refined
using SHELXS-97 and SHELXL-97 programs, respectively.
M.p. 145 8C. Anal. Calc. for C65H97N6NdO2: C, 68.55;
H, 8.60; N, 7.38; Nd, 12.67. Found: C, 68.06; H, 8.59; N,
7.34; Nd, 13.08%. IR (KBr pellet, cmꢃ1): 2924(s),
2851(s), 2665(w), 1636(s), 1601(m), 1481(s), 1447(s),
1346(m), 1315(m), 1257(m), 1072(m), 1026(m), 983(m),
891(m), 771(m), 762(s), 659(m).
4.5. Synthesis of [CyNC(Ph)NCy]3Y×
/
2THF (5)
This complex was prepared from 0.98 g of YCl3 (5.01
mmol), 15.05 mmol of [CyNC(Ph)NCy]Li in 60 ml of
THF using the procedure described above. Colorless
crystals were collected from THF. Yield: 4.3 g (80%).
5. Supplementary material
1
M.p. 153 8C. H-NMR (C6D6, d): 7.18 (m, 15H, Ar),
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 186583 for complex 3, and
186584 for complex 6, respectively. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
3.72 (m, 8H, THF-a-CH2), 3.19 (m, 6H, unique Cy-H),
2.15ꢁ1.14 (m, 60H, C6H10), 1.11 (m, 8H, THF-b-CH2).
/
13C-NMR (C6D6, d): 177.75 (s, NC(Ph)N), 128.50 (m,
C6H5), 68.84 (s, THF-a-CH2), 57.46, 36.70, 26.73, 26.10
(4s, C6H11), 25.85 (s, THF-b-CH2). Anal. Calc. for
C65H97N6O2Y: C, 72.06; H, 9.04; N, 7.76. Found: C,
71.68; H, 8.81; N, 7.52. IR (KBr pellet, cmꢃ1): 2928(s),
2854(s), 1635(s), 1574(m), 1450(m), 1361(m), 1211(s),
1153(s), 1068(m), 891(m), 775(m), 706(m), 669(m),
501(m).
UK (Fax: ꢂ44-1223-336033; e-mail: deposit@ccdc.
/
Acknowledgements
4.6. Synthesis of [CyNC(Ph)NCy]3Yb×
/
2THF (6)
We are indebted to the Chinese National Natural
Science Foundation and the Department of Education
of Jingsu Province for financial support.
This complex was prepared from 1.60 g of YbCl3
(5.73 mmol), 17.01 mmol of [CyNC(Ph)NCy]Li in 60 ml
of THF using the procedure described above. Bright
yellow crystals were collected from toluene solution.
Yield: 5.2 g (78%). M.p. 138 8C. Anal. Calc. for
C65H97N6O2Yb: C, 66.86; H, 8.39; N, 7.20. Found: C,
66.94; H, 8.61; N, 7.17%. IR (KBr pellet, cmꢃ1):
2989(s), 2851(s), 1639(s), 1481(m), 1153(m), 891(m),
789(m), 702(m), 501(w).
References
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4.7. A typical procedure for polymerization reactions
[3] (a) F. Edelmann, Coord. Chem. Rev. 137 (1994) 403;
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The procedures for the polymerization of o-caprolac-
tone are the same (Table 4), and a typical polymeriza-
Luo, Yunjie
