Synthesis of lanthanide chlorides supported by β-diketiminate ligands and molecular structures of L1SmCl2(THF)2 and L2SmCl2(THF)2 [L1 = PhNC(Me)CHC(Me)NPh; L2 = p-ClPh

Article abstract of DOI:10.1016/S0277-5387(02)01367-0

The β-diketiminate lithium salts [L¹Li, L¹ = PhNC(Me)CHC(Me)NPh; L²Li, L² = p-C1PhNC(Me)CHC(Me)NPh(2,6_Pr₂ⁱ)] reacted with anhydrous LnCl₃ (Ln = Sm, Yb) in 1: 1 molar ratio in TH

Full text of DOI:10.1016/S0277-5387(02)01367-0

Polyhedron 22 (2003) 441Á446
/
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Synthesis of lanthanide chlorides supported by b-diketiminate ligands
and molecular structures of L1SmCl2(THF)2 and L2SmCl2(THF)2
[L1ꢀ
/
PhNC(Me)CHC(Me)NPh;
p-ClPhNC(Me)CHC(Me)NPh(2,6-Pri2)]
L2ꢀ
/
Ying-Ming Yao a, Yun-Jie Luo a, Rui Jiao a, Qi Shen a,b,*, Kai-Bei Yu c,
Ling-Hong Weng d
a Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou 215006, PR China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, PR China
c Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610043, PR China
d Department of Chemistry, Fuda University, Shanghai 200433, PR China
Received 7 August 2002; accepted 8 November 2002
Abstract
The b-diketiminate lithium salts [L1Li, L1ꢀ
reacted with anhydrous LnCl3 (LnꢀSm, Yb) in 1:1 molar ratio in THF to afford the new heteroleptic lanthanide complexes
L1LnCl2(THF)2 (LnꢀSm (1), Yb (2)) and L2LnCl2(THF)2 (Lnꢀ
Sm (3), Yb (4)) in high yields. The substituents on the arene ring
/
PhNC(Me)CHC(Me)NPh; L2Li, L2ꢀp-ClPhNC(Me)CHC(Me)NPh(2,6-Pri2 )]
/
/
/
/
have significant effect on the solubility of these complexes. Crystal structure analysis revealed that complexes 1 and 3 are both
monomeric, in which the samarium atom is coordinated by two nitrogen atoms of the b-diketiminate ligand, two chloro and two
THF ligands in distorted octahedral environment.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Synthesis; Crystal structures; Lanthanide; Samarium; Ytterbium; b-Diketiminate ligand
1. Introduction
particular, some of these b-diketiminate complexes have
found potential applications as homogeneous polymer-
In recent years, the use of b-diketiminates (A) as
supporting ligand systems in both main and transition
metal coordination chemistry has attracted considerable
ization catalysts [9Á
diketiminate ligands for the preparation of lanthanide
complexes remains relatively poorly explored [27Á31].
/
16]. However, the utilization of b-
/
attention [1Á25]. These ligands have several attractive
/
features. For example, b-diketiminate ligands and
cyclopentadienyl anions are isoelectronic, and both of
them are monoanions in their deprotonated forms; the
steric and electronic properties of b-diketiminate ligands
can be readily altered through an appropriate choice of
amine and b-diketone used in their synthesis [26]. In
* Corresponding author. Tel.: ꢁ
65112371.
E-mail address: qshen@suda.edu.cn (Q. Shen).
/
86-512-65112513; fax: ꢁ86-512-
/
Recently, we became interested in the synthesis and
reactivity of b-diketiminate lanthanide complexes and
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 3 6 7 - 0

442
Y.-M. Yao et al. / Polyhedron 22 (2003) 441Á446
/
found that replacing one methylcyclopentadienyl by a
(DIPPh)2nacnac group ((DIPPh)2nacnacꢀN,N-diiso-
propylphenyl-2,4-pentanediimine anion, (B)) in
b-diketiminate ligand results in such a dramatic decrease
of its solubility in organic solvents.
In order to increase the solubility of lanthanide b-
diketiminate complex, a more bulky b-diketiminate
ligand, L2H, was synthesized. The reaction of its lithium
/
(CH3C5H4)[(DIPPh)2nacnac]YbNPh2 results in a dra-
matic decrease of catalytic activity for the polymeriza-
tion of methyl methacrylate. We attribute this drop to
the steric congestion around the metal center brought
about by the bulky (DIPPh)2nacnac ligand [32]. In order
to further study the effect of b-diketiminate ligands on
the structure and reactivity of lanthanide complexes, we
salt with anhydrous LnCl3 (LnꢀSm, Yb) in THF at
/
room temperature gave, after 48 h, a bright yellow or
red solution of L2SmCl2 or L2YbCl2, respectively. After
workup, the yellow (for complex 3) or red (for complex
4) microcrystals were obtained in high yields which were
used two less bulky b-diketiminate ligands L1H [L1ꢀ
/
identified to be L2LnCl2(THF)2 (Lnꢀ
Sm (3), Yb (4))
/
PhNC(Me)CHC(Me)NPh] and p-
L2H [L2ꢀ
/
by elemental analyses (C, H, N and Ln) and IR spectra,
as shown in Scheme 2.
ClPhNC(Me)CHC(Me)NPh(2,6-Pri2 )] as reactants and
synthesized four b-diketiminate lanthanide dichlorides,
which serve as important precursors for further trans-
formation. Herein, we report the synthesis and char-
acterization of these complexes and the crystal
structures of L1SmCl2(THF)2 (1) and L2SmCl2(THF)2
(3).
As expected, complexes 3 and 4 are quite soluble in
THF, and moderately soluble in toluene. These results
indicate that selected suitable substituents on the arene
ring of b-diketiminate ligand can efficiently improve the
solubility of b-diketiminate lanthanide complex. Com-
plexes 1Á4 are slightly sensitive to air and moisture, and
/
the crystals can be exposed in air for a few hours
without apparent decomposition.
2. Results and discussion
2.2. Crystal structure of L1SmCl2(THF)2 (1) and
L2SmCl2(THF)2 (3)
2.1. Synthesis
One equiv. of L1Li was added to a slurry of LnCl3
Since the structures of (L)LnCl2(THF)2 derivatives
(where L is a b-diketiminate ligand) have seldom been
reported [29], the structures for complexes 1 and 3 were
determined. Both complexes 1 and 3 have monomeric
structure in the solid state. The two THF molecules in
complex 3 are disordered due to strong thermal motion.
The molecular structures of complexes 1 and 3 are
shown in Figs. 1 and 2, and their selected bond lengths
and angles are listed in Tables 1 and 2, respectively. The
coordination geometries around samarium atoms in
complexes 1 and 3 are similar, and each samarium
atom is six-coordinate with two nitrogen atoms of the b-
diketiminate ligand, two chloro, and two THF ligands
in a distorted octahedron. The molecular structures
establish cis disposition of the THF ligands, and trans
disposition of the chlorine atoms.
(Lnꢀ
/
Sm, Yb) in tolueneÁTHF mixed solvent at room
/
temperature. The color of the solution gradually chan-
ged to yellow (for Sm) or red (for Yb), and yellow or red
precipitate appeared at the same time. After work up,
the yellow (for complex 1) or red (for complex 2)
precipitate was collected by centrifugation. The compo-
sitions of complexes 1 and 2 were established as
L1LnCl2(THF)2 (Lnꢀ
Sm (1), Yb (2)) by elemental
/
analyses (C, H, N and Ln) (Scheme 1). The IR spectra of
complexes 1 and 2 exhibited strong absorptions near
1554 and 1532 cmꢂ1, which were consistent with partial
CÄ/N double bond character [33].
Complexes 1 and 2 are slightly soluble in THF. Due
to their sparing solubility in THF, they can be pre-
cipitated from the reaction mixture in high yield (81Á
/
85%). This behavior is quite different from that of
[(DIPPh)2nacnac]YbCl2(THF)2, which is very soluble in
THF [32]. It is really unexpected that replacing the
diisopropylphenyl groups by the phenyl groups on the
In complex 1, the b-diketiminate ligand is asymme-
trically coordinated to the samarium atom, such that the
˚ ˚
Sm(1)Ã
/
N(2) distance (2.37(1) A) is about 0.08 A longer
˚
N(1) distance (2.29(1) A). This is similar
than the Sm(1)Ã
/
Scheme 1.

Y.-M. Yao et al. / Polyhedron 22 (2003) 441Á
/446
443
Scheme 2.
Table 1
˚
Selected bond lengths (A) and angles (8) in complex 1
Bond lengths
Sm(1)Ã
Sm(1)Ã
Sm(1)Ã
N(1)Ã
C(1)ÃC(2)
/
O(1)
O(2)
Cl(2)
2.34(1)
2.29(1)
Sm(1)Ã
/
N(1)
N(2)
Cl(1)
2.29(1)
/
Sm(1)Ã
/
2.37(1)
2.541(2)
1.27(2)
1.39(1)
/
2.538(2) Sm(1)Ã
1.30(1)
1.40(1)
/
/
C(1)
N(2)Ã
/
C(3)
/
C(2)ÃC(3)
/
Bond angles
O(2)ÃSm(1)Ã
N(1)ÃSm(1)Ã
N(1)ÃSm(1)Ã
O(2)ÃSm(1)Ã
O(1)ÃSm(1)Ã
O(2)ÃSm(1)Ã
O(1)ÃSm(1)Ã
Cl(2)ÃSm(1)Ã
/
/
N(1)
178.3(4) O(2)Ã
99.3(3) O(2)Ã
79.5(4) O(1)Ã
/
Sm(1)Ã
/
O(1)
N(2)
N(2)
82.5(5)
98.8(3)
177.5(5)
92.4(3)
91.0(4)
91.4(3)
92.8(4)
130.6(9)
/
/
O(1)
N(2)
Cl(2)
Cl(2)
Cl(1)
Cl(1)
/
Sm(1)Ã
/
/
/
/
Sm(1)Ã
/
/
/
87.6(3) N(1)Ã
/
Sm(1)Ã
/
Cl(2)
Cl(2)
Cl(1)
Cl(1)
C(1)
/
/
86.9(3) N(2)Ã
/
Sm(1)Ã
Sm(1)Ã
Sm(1)Ã
ZC(2)Ã
/
/
/
88.7(4) N(1)Ã
89.4(3) N(2)Ã
175.1(2) C(3)Ã
/
/
/
/
/
/
/
/Cl(1)
/
/
central metal [27]. The average SmÃ
/
N bond length is
˚
2.33(1) A, which is apparently shorter than the average
Fig. 1. Molecular structure of L1SmCl2(THF)2.
1
N bond length in L3 Sm (2.466(8) A) [27]. This can
˚
SmÃ
/
be attributed to steric congestion around samarium
atom in the latter. Subtraction of the effective ionic
to that found in [(DIPPh)2nacnac]ScCl2(THF) [29], but
different from that in L1GdBr2(THF)2, in which two
nitrogen atoms are symmetrically coordinated to the
3ꢁ
˚
radius (0.958 A) [34] for six-coordinate Sm
from the
Fig. 2. Molecular structure of L2SmCl2(THF)2. Each disordered THF ligand is shown in two possible orientations.

444
Y.-M. Yao et al. / Polyhedron 22 (2003) 441Á446
/
Table 2
latter due to the bulky substituents on one arene ring.
The N(1)ÃSm(1)ÃN(2) angle is 77.54(9)8, which is
comparable with those in complex 1, L1GdBr(THF)2
and L13 Ln (Lnꢀ
Sm, Gd) [27].
˚
Selected bond lengths (A) and angles (8) in complex 3
/
/
Bond lengths
/
Sm(1)Ã
Sm(1)Ã
Sm(1)Ã
N(1)Ã
C(7)ÃC(8)
Bond angles
O(2)ÃSm(1)Ã
N(1)ÃSm(1)Ã
N(1)ÃSm(1)Ã
O(2)ÃSm(1)Ã
O(1)ÃSm(1)Ã
O(2)ÃSm(1)Ã
O(1)ÃSm(1)Ã
Cl(2)ÃSm(1)Ã
/
O(1)
O(2)
Cl(2)
2.463(2)
2.477(2)
2.628(1)
1.332(4)
1.402(4)
Sm(1)Ã
Sm(1)Ã
Sm(1)Ã
N(2)Ã
C(8)ÃC(9)
/
N(1)
N(2)
Cl(3)
2.398(2)
2.387(3)
2.638(1)
1.331(4)
1.392(4)
/
/
/
/
/
C(9)
/
C(7)
3. Experimental
/
/
Reactions were performed under pure Ar with exclu-
sion of air and moisture by Schlenk techniques. Solvents
were dried and freed of oxygen by refluxing over sodium
or sodium benzophenone ketyl and distilled under Ar
prior to use. Anhydrous LnCl3 [35] and L1Li [26] were
prepared according to the literature methods.
Melting points were determined in sealed Ar-filled
capillaries and are uncorrected. Metal analyses were
carried out using complexometric titration. Carbon,
hydrogen, and nitrogen analyses were performed by
direct combustion on a Carlo Erba-1110 instrument;
quoted data are the average of at least two independent
determinations. The IR spectra were recorded on a
Nicolet-550 FTIR spectrometer as KBr. 1H NMR
spectra were recorded on a Unity Varian-400 spectro-
meter.
/
/
N(1)
171.92(8) O(2)Ã
100.12(8) O(2)Ã
77.54(9) O(1)Ã
/
Sm(1)Ã
/
O(1)
N(2)
N(2)
87.34(9)
95.36(9)
173.54(8)
94.03(6)
95.58(7)
98.81(6)
93.06(7)
131.4(3)
/
/
O(1)
N(2)
Cl(2)
Cl(2)
Cl(3)
Cl(3)
/
Sm(1)Ã
/
/
/
/
Sm(1)Ã
/
/
/
82.72(6) N(1)Ã
90.58(6) N(2)Ã
/
Sm(1)Ã
/
Cl(2)
Cl(2)
Cl(3)
Cl(3)
/
/
/
Sm(1)Ã
Sm(1)Ã
Sm(1)Ã
C(8)Ã
/
/
/
85.30(6) N(1)Ã
81.30(7) N(2)Ã
165.82(3) C(7)Ã
/
/
/
/
/
/
/
/Cl(3)
/
/C(9)
˚
N distance gives 1.371 A, which is slightly
average SmÃ
/
1
shorter than those in L GdBr2(THF)2 (1.428 A) [27] and
˚
˚
[(DIPPh)2nacnac]ScCl2(THF) (1.456 A) [29], but com-
parable with that in (MeC5H4)[(DIPPh)2nacnac]YbCl
˚
Cl bond lengths are 2.538(2)
(1.375 A) [32]. Two SmÃ
/
˚
and 2.541(2) A, which are slightly shorter than the
corresponding distances in [(DIPPh)2nac-
nac]ScCl2(THF) [29] even when the difference in ionic
radii is considered.
3.1. Synthesis of 2-(2,6-diisopropylphenyl)aminopent-2-
en-4-one (5)
The bond distances of C(1)Ã
/
C(2), C(2)Ã
/
C(3), N(1)Ã
/
C(1) and N(2)ÃC(3) lie intermediate between the
/
corresponding single- and double-bond distances (see
Table 1), which suggest significant delocalization within
A 20.0 mL amount of 2,6-diisopropylaniline (0.106
mol) was added to a solution of 2,4-pentanedione (16.4
mL, 0.159 mol) in C6H5CH3 (100 mL) in a round-
bottomed flask. The resulting mixture was heated to
reflux for 4 h, and water was removed as a C6H5CH3
azeotrope using a Dean and Stark apparatus. The
reaction mixture was then evaporated to dryness. The
resulting solid was recrystallized from C6H14 to afford 2-
(2,6-diisopropylphenyl)aminopent-2-en-4-one (5) (23.9
g, 87%). 1H NMR (400 MHz, CDCl3): 1.14 (d, 6H,
CH3CHCH3), 1.20 (d, 6H, CH3CHCH3), 1.64 (s, 3H,
the p-system of b-diketiminate backbone. The SmÃ
2, 3) distances are quite long, suggesting a negligible p
contribution to the b-diketiminate-Sm bonding in this
compound. The N(1)Ã
which is more acute than the corresponding angles
in complexes [(DIPPh)2nacnac]ScCl2(THF), [29]
/
C(1,
/
Sm(1)ÃN(2) angle is 79.5(4)8,
/
and
nacnac](THF)}×
In complex 3, the b-diketiminate ligand is symmetri-
{[(DIPPh)2nacnac]YbCl(m-Cl)3Yb[(DIPPh)2-
/
1/2MePh [32].
cally coordinated to the samarium atom with SmÃ
/
N
CH3), 2.13 (s, 3H, CH3), 2.99Á
CH3CHCH3), 5.21 (s, 1H, CH ÄC(CH3)N), 7.18 (d,
2H, aromatic protons), 7.28Á7.32 (m, 1H, aromatic
proton), 12.06 (s, 1H, NH).
/3.06 (m, 2H,
˚
bond lengths of 2.398(2) and 2.387(3) A, which is
different from that in complex 1. Moreover, the average
/
/
˚
N bond length of 2.392(3) A in 3 is apparently
SmÃ
/
longer than that in 1, although both complexes have
similar coordination geometry. However, this value is
still comparable with those in L1GdBr2(THF)2 [27] and
[(DIPPh)2nacnac]ScCl2(THF) [29] when the difference
3.2. Synthesis of 2-(2,6-diisopropylphenyl)aminopent-2-
en-4-(p-chlorophenyl)imine (L2H) (6)
in ionic radii is considered. The long distances of SmÃ
/
p-Chloroaniline hydrochloride (12.6 g, 0.077 mol),
compound 5 (20 g, 0.077 mol), and 100 ml of absolute
EtOH were added to a 250 ml round-bottomed flask.
The reaction mixture was allowed to reflux for 4 h. The
reaction solution was then evaporated to dryness. After
stirring with 40 ml saturated Na2CO3, 2-(2,6-diisopro-
pylphenyl)aminopent-2-en-4-(p-chlorophenyl)imine
(L2H) was extracted into ethyl ether. Evaporation of
solvent and recrystallization from C6H14 afforded L2H
C(7, 8, 9) reveal that the b-diketiminate ligand is
coordinated to the samarium atom in an h2 manner.
There is the expected pattern of delocalization within the
SmNC3N six-membered ring. The average SmÃ
/
Cl and
SmÃO(THF) bond lengths in complex 3 are about 0.10
/
˚
and 0.16 A longer than those in complex 1, respectively.
It is reasonable to ascribe these differences in bond
parameters to the increased steric congestion in the

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
or www: http://www.ccdc.cam.ac.uk).

446
Y.-M. Yao et al. / Polyhedron 22 (2003) 441Á446
/
[6] L. Kakaliou, W.J. Scanlon, IV, B. Qian, S.W. Baek, M.R. Smith,
III, D.H. Motry, Inorg. Chem. 38 (1999) 5964.
Table 3
Crystal data and experimental parameters
[7] M. Rahim, N.J. Taylor, S. Xin, S. Collins, Organometallics 17
(1998) 1315.
Compound
1
3
[8] V.C. Gibson, J.A. Segal, A.J.P. White, D.J. Williams, J. Am.
Chem. Soc. 122 (2000) 7120.
Formula
C25H33Cl2N2O2Sm C31H44Cl3N2O2Sm
614.78
298(2)
Molecular weight
Temperature (K)
Crystal system
733.38
293(2)
[9] V.C. Gibson, P.J. Maddox, C. Newton, C. Redshaw, G.A. Solan,
A.J.P. White, D.J. Williams, J. Chem. Soc., Chem. Commun.
(1998) 1651.
orthorhombic
yellow, prism
Pna2(1)
monoclinic
yellow, prism
P2(1)/c
Crystal color and habit
Space group
Unit cell dimensions
[10] W.K. Kim, M.J. Fevola, L.M. Liable-Sands, A.L. Rheingold,
K.H. Theopold, Organometallics 17 (1998) 4541.
[11] R. Vollmerhaus, M. Rahim, R. Tomaszewski, S. Xin, N.J. Taylor,
S. Collins, Organometallics 19 (2000) 2161.
˚
a (A)
19.642(5)
9.573(3)
14.082(4)
90
9.130(1)
25.037(4)
14.840(2)
97.33(1)
3364.5(8)
4
˚
b (A)
[12] A.P. Dove, V.C. Gibson, E.L. Marshall, A.J.P. White, D.J.
Williams, J. Chem. Soc., Chem. Commun. (2001) 283.
[13] M. Cheng, D.R. Moore, J.J. Reczek, B.M. Chamberlain, E.B.
Lobkovsky, G.W. Coates, J. Am. Chem. Soc. 123 (2001) 8738.
[14] B.M. Chamberlain, M. Cheng, D.R. Moore, T.M. Ovitt, E.B.
Lobkovsky, G.W. Coates, J. Am. Chem. Soc. 123 (2001) 3229.
[15] M. Cheng, A.B. Attygalle, E.B. Lobkovsky, G.W. Coates, J. Am.
Chem. Soc. 121 (1999) 11583.
˚
c (A)
b (8)
3
V (A )
˚
2648.0(12)
4
1.542
Z
Dcalc (g cmꢂ3
)
1.448
2.012
1492
m (mmꢂ1
F(000)
)
2.442
1236
Crystal size (mm)
umax (8)
Reflections collected
0.25ꢃ
/
0.20ꢃ
/
0.15 0.48ꢃ
/
0.44ꢃ0.34
/
[16] M. Cheng, E.B. Lobkovsky, G.W. Coates, J. Am. Chem. Soc. 120
(1998) 11018.
27.52
12 872
2.0s(I) 4274
25.01
6695
4635
5919
383
[17] X. Dai, T.H. Warren, J. Chem. Soc., Chem. Commun. (2001)
1998.
Reflections with I ]
Independent reflections
Parameters refined
/
5648
290
[18] P.H.M. Budzelaar, R. Gelder, A.W. Gal, Organometallics 17
(1998) 4121.
R
0.0469
0.0981
0.0265
0.0393
[19] P.J. Bailey, R.A. Coxall, C.M. Dick, S. Fabre, S. Parsons,
Organometallics 20 (2001) 798.
wR2
[20] Y. Ding, H.W. Roesky, M. Noltemeyer, H.G. Schmidt, P.P.
Power, Organometallics 20 (2001) 1190.
[21] A.E. Ayers, T.M. Klapotke, H.V.R. Dias, Inorg. Chem. 40 (2001)
1000.
Acknowledgements
[22] F. Cosledan, P.B. Hitchcock, M.F. Lappert, J. Chem. Soc.,
Chem. Commun. (1999) 705.
Financial support from the Chinese National Natural
Science Foundation, the Education Department of
Jiangsu Province and the Key Laboratory of Organic
Synthesis of Jiangsu Province is gratefully acknowl-
edged.
[23] J. Prust, A. Stasch, W. Zheng, H.W. Roesky, E. Alexopoulos, I.
Uson, D. Bohler, T. Schuchardt, Organometallics 20 (2001) 3825.
[24] M. Stender, B.E. Eichler, N.J. Hardman, P.P. Power, J. Prust, M.
Noltemeyer, H.W. Roesky, Inorg. Chem. 40 (2001) 2794.
[25] A. Akkari, J.J. Byrne, I. Saur, G. Rima, H. Gornitzka, J. Barrau,
J. Organomet. Chem. 622 (2001) 190.
[26] J.E. Parks, R.H. Holm, Inorg. Chem. 7 (1968) 1408.
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Organometallics 18 (1999) 2947.
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