Heterobimetallic complexes of lanthanide and lithium metals with dianionic guanidinate ligands: Syntheses, structures and catalytic activity for amidation of aldehydes with amines

Article abstract of DOI:10.1016/j.jorganchem.2009.12.010

Reactions of triguanidinate lanthanide complexes Ln[(ⁱPrN)(NC₆H₄p-Cl)C(NHⁱPr)]₃ (Ln = Nd, Y) with 3 equiv. of n-BuLi gave [Li(THF)(DME)]₃Ln[μ-η²η¹ (ⁱPrN)₂C(NC₆H₄p-Cl)]₃, which represents the first structurally characterized complexes of lanthanide and lithium metals with dianionic guanidinate ligands. The Nd complex was found to be an effective catalyst for amidation of aldehydes with amines under mild conditions with a wide scope of substrates.

Full text of DOI:10.1016/j.jorganchem.2009.12.010

Journal of Organometallic Chemistry 695 (2010) 747–752
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Heterobimetallic complexes of lanthanide and lithium metals with dianionic
guanidinate ligands: Syntheses, structures and catalytic activity for amidation
of aldehydes with amines
Cunwei Qian a, Xingmin Zhang a, Yong Zhang a, Qi Shen a,b,
*
a Key Laboratory of Organic Synthesis of Jiangsu Province, Department of Chemistry and Chemical Engineering, Dushu Lake Campus, Suzhou University,
Suzhou 215123, People’s Republic of China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Reactions of triguanidinate lanthanide complexes Ln[(iPrN)(NC6H4p-Cl)C(NHiPr)]3 (Ln = Nd, Y) with 3
Article history:
Received 25 October 2009
Received in revised form 10 December 2009
Accepted 11 December 2009
Available online 21 December 2009
equiv. of n-BuLi gave [Li(THF)(DME)]3Ln[l-
g2g1 (iPrN)2C(NC6H4p-Cl)]3, which represents the first struc-
turally characterized complexes of lanthanide and lithium metals with dianionic guanidinate ligands. The
Nd complex was found to be an effective catalyst for amidation of aldehydes with amines under mild
conditions with a wide scope of substrates.
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Heterobimetallic
Lanthanide
Dianionic guanidinate
Catalysis
1. Introduction
in organolanthanide chemistry as ancillary ligands [22–32]. More-
over, trisguanidinate lanthanides complexes can also serve as
Heterobimetallic complexes of lanthanide and alkali metals are
of interest because they have proven to enable transformations
that have never been accomplished using monometallic analogs
of lanthanide by virtue of cooperative effects between the two dif-
ferent metals [1–3]. For example, the heterobimetallic binaphthox-
ide and phenoxide complexes of lanthanide and alkali metals have
been explored to be versatile asymmetric catalysts in organic syn-
theses [1–9]. Various organometallic complexes of trivalent lan-
thanide and alkali metals [10–17], as well as the complexes of
divalent lanthanide and sodium metals [18,19] have proven to be
more effective catalysts in polymerization of nonpolar and polar
monomers than their corresponding lanthanide complexes with-
out alkali metals. Recently, we have addressed that phenoxides
[20] and bridged bisamidinate complexes [21] of lanthanide and
alkali metals are much more active catalysts for amidation of alde-
hydes with amines under mild conditions in comparison with their
monolanthanide partner. Now we are particularly interested in
synthesis and reactivity of bimetallic complexes with guanidinate
ligands because monoanionic guanidinates have widely been used
effective catalysts for polymerization of lactone [33–35] and for
amidation of aldehydes with amines [36]. Considering the ability
to generate dianionic species by deprotonating of a second N–H
bond which provides the possibility to construct a new kind of het-
erobimetallic complex [37], the N,N0,N00-trialyl guanidinato ligands
were chosen. While various complexes of d-block transition metals
and s-block main metals with dianionic N,N0,N00-trialyl guanidi-
nates ligands were synthesized [37–44], no example of lanthanide
metals has been reported up to date. Here we report the syntheses
and molecular structures of the first heterobimetallic complexes of
lanthanide and lithium metals with dianionic guanidinate ligands
[Li(THF)(DME)]3Ln[l-
g2g1 (iPrN)2C(NC6H4p-Cl)]3 (Ln = Nd, Y).
Their high activity for mild amidation of aldehydes with amines
was also presented.
2. Results and discussion
2.1. Syntheses of complexes 1–6 and molecular structures of
complexes 3–6
* Corresponding author. Address: Key Laboratory of Organic Synthesis of Jiangsu
Province, Department of Chemistry and Chemical Engineering, Dushu Lake Campus,
Suzhou University, Suzhou 215123, People’s Republic of China. Tel.: +86 512
65880306; fax: +86 512 65880305.
Reaction of anhydrous LnCl3 (Ln = Nd, Y) with 3 equiv. of in situ
formed lithium guanidinate Li[(iPrN)(NC6H4p-Cl)C(NHiPr)] 1 by
reaction of lithium amide LiNHC6H4p-Cl 2 with N,N-diisopropylcar-
i
E-mail address: qshen@suda.edu.cn (Q. Shen).
bodiimide PrN@C@NiPr in THF at room temperature, afforded the
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.12.010

748
C. Qian et al. / Journal of Organometallic Chemistry 695 (2010) 747–752
DME
THF
Ar
Li
N
N
Ar
N
N
N
Ar
N
N
3 iPrN=C=NiPr, THF
3 n-BuLi
N
(1)
Ln
N
Ln
N
Li
3ArNHLi
N
N
THF, DME
N
LnCl3, THF
(2)
THF
Ar N
Ar
DME
O
THF
Li
N
N
H
DME
Ar
Ln = Nd (5), 75%; Y(6), 62%
Ar = -C6H4p-Cl
Ln = Nd (3), 67%; Y(4), 61%
Scheme 1.
asymmetric triguanidinate complexes by
a
1,3-H shift
[Li(THF)(DME)]3Ln[l-
g2g1 (iPrN) (NC6H4p-Cl)C(NiPr)]3(Ln = Nd,
Ln[(iPrN)(NC6H4p-Cl)C(NHiPr)]3THF (Ln = Nd, 3; Y, 4) as blue crys-
tals for 3 and as colorless crystals for 4 (Scheme 1). Complex 3
was further confirmed by single-crystal X-ray analysis (Fig. 1).
The selected bond lengths and angles are listed in Table 1. The
molecular structure of 3 is quite similar to that of analogous La
complex [36], in which the central Nd ion is bound to three chelat-
ing asymmetric guanidinates and coordinated to one THF molecule
in a capped octahedron. The average Nd–N bond distance of
2.492(6) Å is in the range for the published analogues [7] and the
C–N distances within the chelate rings (av. 1.345(5) Å) are consis-
tent with partial double bond character.
Y). Obviously complexes 5 and 6 are derived from triple deprotona-
tion followed by the rearrangement. The occurrence of the rear-
rangement may make these complexes more stable.
Complexes 5 and 6 are isostructural. The selected bond lengths
and angles are listed in Table 1. The coordination sphere around
each metal center is composed of six nitrogen atoms from the three
dianionic ligands to form a distorted octahedron. The third nitro-
gen atom of each guanidinate (N3, N6 and N9) lies outside of the
metal coordination sphere, but bonds to each lithium ion (Li1,
Li2 and Li3) (Fig. 2). The three Li–N bond distances in both 5 and
6 are comparable and the average distances of 1.978(16) Å for 5
and 1.996(17) Å for 6 are in the range of single Li–N bond (1.96
Å). The values are also comparable to those found in lithium
amides [Li(N(TMS)2]3) [45,46] and [{Li(N(TMS)2}(OEt2)]2 [45]. Fur-
thermore, the average C–N(Li) (C6H4p-Cl) bond distances of
1.405(9) Å for 5 and 1.396(9) Å for 6 are consistent with a CN single
The reaction of 3 and 4 with 3 equiv. of n-BuLi, respectively, was
then tried in an attempt to synthesize heterobimetallic complexes
with dianionic guanidinates ligands by deprotonation of N–H
bond. The reaction went rapidly at room temperature in THF.
Removing the THF and extracting the residue with toluene resulted
in the isolation of complexes 5 and 6 in moderate yields upon crys-
tallization from a mixture of toluene and DME at room tempera-
ture. Single crystal X-ray analysis of these new products showed
they to be the heterobimetallic complexes with formula
bond. Such a
l-
g2g1 coordination mode for a dianionic guanidi-
nate has not been found previously. Each four-membered metalla-
cycle Ln–N–C–N for both complexes is planar. The Ln–N bond
distances vary from 2.437(6) to 2.505(6) Å for 5 and 2.329(6) to
2.410(6) Å for 6, and the average distances of 2.471(6) Å for 5
and 2.338(6) Å for 6 are almost consistent with 2.492(6) Å in 3
[Li(THF)(DME)]3Ln [
6) (Scheme 1), not the asymmetric guanidinate complexes
l-
g2g1(iPrN)2C(NC6H4p-Cl)]3 (Ln = Nd, 5; Y,
Fig. 1. The molecular structure of complex 3. Hydrogen atoms are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability level.

C. Qian et al. / Journal of Organometallic Chemistry 695 (2010) 747–752
749
Table 1
Table 2
Selected bond lengths (Å) and angles (°) for 3, 5 and 6.
Optimization of complexes 1–6 catalyzed amidation of aldehydes with amines.a
3
5
6
NH2
CHO
NH C
O
9aa
Cat.
Nd(1)–N(1)
Nd(1)–N(2)
Nd(1)–N(4)
Nd(1)–N(5)
Nd(1)–N(7)
Nd(1)–N(8)
Nd(1)–N(8)
N(1)–C(1)
2.486(6)
2.507(6)
2.487(6)
2.455(6)
2.496(6)
2.518(6)
1.358(9)
1.331(9)
1.382(9)
1.382(9)
1.319(9)
1.348(9)
1.332(9)
2.551(5)
1.376(9)
1.372(9)
1.385(9)
Ln(1)–N(1)
Ln(1)–N(2)
Ln(1)–N(4)
Ln(1)–N(5)
Ln(1)–N(7)
Ln(1)–N(8)
N(1)–C(1)
N(2)–C(1)
N(4)–C(22)
N(5)–C(22)
N(7)–C(43)
N(8)–C(43)
N(3)–C(1)
N(6)–C(22)
N(9)–C(43)
N(3)–Li(1)
N(6)–Li(2)
N(9)–Li(3)
2.486(6)
2.437(6)
2.447(6)
2.505(6)
2.488(6)
2.461(5)
1.360(9)
1.340(9)
1.341(9)
1.338(9)
1.339(9)
1.344(9)
1.399(9)
1.409(9)
1.406(9)
2.376(7)
2.329(6)
2.358(6)
2.394(6)
2.410(6)
2.359(5)
1.324(9)
1.365(9)
1.353(9)
1.347(9)
1.354(9)
1.356(9)
1.385(9)
1.399(10)
1.403(9)
+
25°C, THF
7a
8a
Entry
Cat. (mol%)
Yield (%)
Entry
Cat. (mol%)
Yield (%)b
N(2)–C(1)
1
2
3
1 (3%)
2 (3%)
3 (2%)
30
27
42
4
5
6
4 (2%)
5 (1%)
6 (1%)
30
92
80
N(4)–C(14)
N(5)–C(14)
N(7)–C(27)
N(8)–C(27)
Nd(1)–O(1)
N(3)–C(1)
a
Starting amine, aldehyde, and catalyst concentrations are 0.02 mmol/mL in
each experiment; amine/aldehyde = 1/3.
b
Isolated yields based on aniline.
N(6)–C(14)
N(9)–C(27)
1.977(16) 2.009(17)
1.968(16) 2.005(15)
1.99(2)
1.973(19)
2.2. Catalytic activity of complexes 1–6 for amidation reactions of
aldehydes with amines
N(1)–Nd(1)–N(2)
N(5)–Nd(1)–N(4)
N(7)–Nd(1)–N(8)
C(1)–N(1)–Nd(1)
C(1)–N(2)–Nd(1)
C(14)–N(4)–Nd(1) 93.7(4)
C(14)–N(5)–Nd(1) 96.8(5)
C(27)–N(7)–Nd(1) 96.9(4)
C(27)–N(8)–Nd(1) 96.3(5)
54.1(2)
54.5(2)
N(2)–Ln(1)–N(1)
N(4)–Ln(1)–N(5)
54.45(19) 56.6(2)
53.93(19) 56.3(2)
54.01(19) 56.63(19)
53.08(19) N(8)–Ln(1)–N(7)
95.3(5)
95.1(5)
C(1)–N(1)–Ln(1)
C(1)–N(2)–Ln(1)
C(22)–N(4)–Ln(1) 97.3(4)
C(22)–N(5)–Ln(1) 94.8(4)
C(43)–N(7)–Ln(1) 95.0(4)
C(43)–N(8)–Ln(1) 96.0(4)
N(2)–C(1)–N(1)
N(5)–C(22)–N(4)
N(7)–C(43)–N(8)
94.4(4)
97.1(4)
94.9(4)
95.9(4)
96.4(4)
95.0(4)
93.6(4)
95.8(4)
112.0(7)
112.3(6)
113.2(6)
To further address the reactivity of these new heterobimetallic
complexes, amidation of aldehydes with amines under mild condi-
tions were examined with them as amides are important structural
units in many biologically and pharmaceutically active com-
pounds. The catalytic activity of 5 and 6 for amidation of benzalde-
hyde 7a with aniline 8a was first tested in THF at 25 °C. For control
the same reaction with complexes 1–4, respectively, was also con-
ducted. As shown in Table 2, bimetallic complexes 5 and 6 are
much more active than the corresponding monometallic complex
3 and 4: the amide 9aa is produced in the yield of 92% for 5 and
80% for 6 at the catalyst loading of 1 mol% while only 42% for 3
and 30% yield for 4 at the catalyst loading of 2 mol%. The two lith-
ium complexes 1 and 2 are both less active (Table 2, entries 1 and
2). The high activity of heterobimetallic complexes may result from
the cooperative effects by lanthanide and Li metals. Preliminary
results also showed that complex 5 is a very robust and effective
N(2)–C(1)–N(1)
N(5)–C(14)–N(4)
N(8)–C(27)–N(7)
115.1(7)
113.8(7)
113.5(7)
113.1(6)
113.9(6)
113.8(6)
when the differences in ionic radium was considered [47]. The C–N
bond distances within the guanidinate fragment are indicative of
delocalized p-bond (av. 1.344(9) Å for 5 and 1.350(9) Å for 6).
The coordination geometry around each Li ion is a tetrahedron
by one nitrogen atom and additional three oxygen atoms from one
THF and one DME molecules with a normal Li–O bond distance (av.
2.056 Å for 5 and 2.050 Å for 6).
Fig. 2. The molecular structure of complex 5 (LN1 = Nd) and 6 (LN1 = Y). Hydrogen atoms are omitted for clarity, and thermal ellipsoids are drawn at the 30% probability level.

750
C. Qian et al. / Journal of Organometallic Chemistry 695 (2010) 747–752
catalyst with good functional group tolerance and a wide scope of
substrates (Table 3). Less electrophilic cyclohexanal and less nucle-
ophilic secondary cyclic amines, pyrrolidine, piperidine, and mor-
pholine, also offered good to excellent yields at 1 mol% catalyst
loading (Table 3), indicating that 5 is the most effective catalyst
ever known [20,21,36,48]. It was supposed that one of the interme-
diates for the amidation might be an amide by the amination of
complex 5(6) with amine according to the mechanism presented
[48]. An attempt to isolate the amide was not successful yet. The
work on it is going on.
3. Conclusion
We have described the syntheses and structures of the first het-
erobimetallic complexes of Ln and Li with dianionic guanidinates
[Li(THF)(DME)]3Ln[l-
g2g1 (iPrN)2C(NC6H4p-Cl)]3 (Ln = Nd, Y) via
deprotonation of second N–H bond followed by the rearrangement.
The Nd complex can serve as an effective catalyst for mild amida-
tion of aldehydes with amines.
Table 3
Complex 5 catalyzed amidation of aldehydes with amines.a
O
R2
R1
R2
O
4. Experimental section
1 mol % 5
R
N
+
o
N
H
8
THF, 25 C, 3 h
R1
R
H
4.1. General procedures
9
7
All manipulations and reactions were performed under a puri-
fied argon atmosphere using standard Schlenk techniques. Sol-
vents were degassed and distilled from sodium benzophenone
ketyl prior to use. [(ArN)C(NiPr)(HNiPr)]3Ln [Ar = p-ClPh, Ln = Nd
(3), Ln = Y (4)] [(ArNLi)C(NiPr)2]3Ln [Ar = p-ClPh, Ln = Nd (5),
Ln = Y (6)] were prepared. All aldehydes and amines were predried,
sublimed, recrystallized or distilled before use. Melting points
were determined in sealed Ar-filled capillary tube, and uncor-
rected. 1H and 13C NMR spectra were recorded on a Unity Inova-
400 spectrometer. Chemical shifts (d) were reported in ppm.
Entry Aldehyde
1
Amine
Acylmide
Yield
(%)b
92
88
90
O
O
HN
CHO
N
O
7a
7a
8b
9ab
2
3
O
N
CHO
HN
8c
9ac
4.2. Synthesis of [iPrNHCNiPr(NC6H4p-Cl)]3NdꢀTHF (3)
O
NH
CHO
CHO
N
A
Schlenk flask was charged with p-ClC6H4NH2 (1.905 g,
7a
7a
8d
9ad
15.0 mmol), THF (30 mL), and a stir bar. The solution was cooled
to 0 °C, and n-BuLi (8.6 mL, 15.0 mmol, 1.75 M in hexane) was
added, then slowly warmed to room temperature and stirred for
1 h. To this solution was added N,N0-diisopropylcarbodiimide
(2.4 mL, 15.3 mmol) at 0 °C. The resulting solution was slowly
warmed to room temperature and stirred for 1 h and then added
slowly to a blue slurry of NdCl3 (1.22 g, 5.0 mmol) in 20 mL THF.
The color of the solution immediately changed to blue. The result-
ing solution was then stirred for another 24 h and evaporated to
dryness in vacuo. The residue was extracted with Et2O and LiCl
was removed by centrifugation. The extracts were concentrated
and cooled to 0 °C for crystallization, to afford blue crystals. Yield:
3.26 g (67%). Mp: 180–182 °C. Anal. Calc. for C43H65Cl3N9NdO
(974.63): C, 52.99; H, 6.72; N, 12.93; Nd, 14.80. Found: C, 53.00;
4
80
O
F
NH2
N
H
F
8e
9ae
9bc
5
6
87
91
O
CHO
HN
N
7b
8c
O
NH2
Cl
CHO
N
H
Cl
9ca
7c
8a
7
8
97
91
O
O
O
HN
Cl
CHO
CHO
N
H, 6.61; N, 13.01; Nd, 14.71%. IR (KBr pellet): 3320 (s) cmꢁ1
,
O
Cl
9cb
3061 (s), 2981 (s), 2910 (s), 2888 (s), 1635 (s), 1577 (s), 1520 (s),
1421 (s), 1370 (s), 1328 (s), 1165 (m), 1123 (m), 1034 (m), 940 (m).
7c
8b
Cl
HN
N
Cl
9cc
4.3. Synthesis of [iPrNHCNiPr(NC6H4p-Cl)]3YꢀTHF (4)
7c
8c
9
90
90
O
CHO
HN
Following the procedure similar to that for the synthesis of 3,
N
complex Li[iPrNHCNiPr(NC6H5)] (15.0 mmol), which was formed
i
in situ by the reaction of LiNHC6H5 with PrN@C@NiPr, reacted
7d
8c
9dc
10
O
O
with YCl3 (0.975 g, 5.0 mmol), in THF (60 mL) to yield the colorless
crystals (4) upon crystallization from ether. Yield: 2.80 g (61%). 1H
NMR (400 MHz, C6D6): 7.35–7.31 (m, 6H, m-H–Ph), 6.93–6.74 (m,
NH2
O
O
N
H
CHO
CHO
7e
8a
9ea
6H, o-H–Ph), 3.64–3.50 (m, 7H, a-H-THF and N–H), 3.32–3.17 (m,
11
90
O
O
HN
O
6H, H–C(N)Me2), 1.48–1.23 (m, 4H, b-H, THF), 0.95–0.78 (d, 36H,
CH3) ppm. Anal. Calc. for C43H65Cl3N9YO (919.33): C, 56.18; H,
7.13; N, 13.71; Y, 9.67. Found: C, 56.07; H, 7.08; N, 13.69; Y,
9.60%. IR (KBr pellet): 3377 (s) cmꢁ1, 3079 (s), 2963 (s), 2924 (s),
2874 (s), 1636 (s), 1578 (s), 1516 (s), 1423 (s), 1363 (s), 1327 (s),
1160 (m), 1122 (m), 1014 (m), 944 (m).
N
O
7e
8b
9eb
a
Starting amine, aldehyde, and catalyst concentrations are identical in each
experiment; amine/aldehyde = 1/3.
b
Isolated yields based on amine.

C. Qian et al. / Journal of Organometallic Chemistry 695 (2010) 747–752
751
4.4. Synthesis of [(p-ClPhNLi)C(NiPr)2]3Ndꢀ3THFꢀ3DME (5)
Table 4
Details of the crystallographic data and refinements for complexes 3, 5 and 6.
A
Schlenk flask was charged with [iPrNHCNiPr(NC6H4p-
3
5
6
Cl)]3NdꢀTHF (2.92 g, 3.0 mmol), THF (30 mL), and a stir bar. The
solution was cooled to 0 °C, and n-BuLi (5.1 mL, 9.0 mmol, 1.75 M
in hexane) was added, then slowly warmed to room temperature
and stirred for 24 h. The resulting solution was then evaporated
to dryness in vacuo. DME (15 mL) and toluene (5 mL) was added
to the residue and then heated until to the solution being clear.
The solution was cooled to room temperature for crystallization
and the blue crystals (5) was isolated. Yield: 3.17 g (75%). Mp:
230–228 °C. Anal. Calc. for C63H108Cl3Li3N9O9Nd (1406.99): C,
53.78; H, 7.74; N, 8.96; Nd, 10.25. Found: C, 53.67; H, 7.72; N,
8.95; Nd, 10.21%. IR (KBr pellet): 3074 (s) cmꢁ1, 2974 (s), 2926
(s), 2869 (s), 1636 (s), 1609 (s), 1585 (s), 1546 (s), 1499 (s), 1485
(s), 1365 (m), 1165 (m), 1091 (m), 1007 (m), 952 (m), 859(m).
Empirical
formula
Fw
Temperature 223(2)
(K)
k (Å)
Crystal
system
Space group
C43H65Cl3N9NdO C63H108Cl3Li3N9NdO9 C63H108Cl3Li3N9O9Y
974.63
1406.99
223(2)
1351.66
223(2)
0.71075
Triclinic
0.71075
Monoclinic
0.71075
Monoclinic
ꢀ
P21/c
P21/c
P1
a (Å)
b (Å)
c (Å)
10.375(3)
13.052(4)
18.016(5)
80.124(7)
89.943(8)
86.812(8)
2399.5(13)
2
19.072(3)
12.2723(18)
35.336(5)
90
94.420(2)
90
19.029(3)
12.0563(19)
35.222(6)
90
94.175(3)
90
a
(°)
b (°)
c
(°)
V (Å3)
Z
8246(2)
4
8059
4
4.5. Synthesis of [(p-ClPhNLi)iPrNCNiPr]3Yꢀ3THFꢀ3DME (6)
Dcalc
1.349
1.133
1.114
(g cmꢁ3
)
l
(mmꢁ1
F (0 0 0)
)
1.290
0.776
0.874
Following the procedure for the synthesis of 5, the reaction of
[iPrNHCNiPr(NC6H4p-Cl)]3YꢀTHF (3.0 mmol) in THF (20 mL) with
n-BuLi (5.1 mL, 9.0 mmol, 1.75 M in hexane) afforded 6 as colorless
crystals upon crystallization from DME and toluene. Yield: 2.51 g
(62%). Mp: 212–210 °C. 1H NMR (400 MHz, TDF): d = 7.01–6.89
(m, 6H, m-H–Ph), 6.55–6.46 (m, 6H, o-H–Ph), 3.66–3.58 (m, 12H,
1010
2964
2880
h Range (°)
No. of rflns
No. of
unique
rflns
3.01–25.50
16 520
8746
3.01–25.50
31 830
15 146
3.00–25.50
46 446
14 767
Rint
0.0689
521
0.0325
728
0.0715
729
a-H-THF), 3.41–3.38 (m, 12H, O–CH2–), 3.33–3.30 (m, 6H, H–
Variables
R[I > 2d(I)]
wR2
1.099
0.1737
1.099
0.0864
0.2391
1.169
0.1308
0.3192
1.141
C(N)Me2), 3.24 (s, 18H, O–CH3), 1.77–1.70 (m, 4H, b-H, THF),
1.10–0.97 (d, 36H, CH3) ppm. 13C NMR (100 MHz, TDF): d = 155.7,
127.7, 123.3, 121.2, 115.8, 71.9, 67.4, 58.1, 45.5, 25.6, 23.3 (Anal.
Calc. for C63H108Cl3Li3N9O9Y (1351.66 ppm): C, 55.98; H, 8.05; N,
9.33; Y, 6.58. Found: C, 55.78; H, 7.82; N, 8.93; Y, 6.56%. IR (KBr pel-
let): 3074 (s) cmꢁ1, 2973 (s), 2926 (s), 2872 (s), 1630 (s), 1600 (s),
1585 (s), 1542 (s), 1500 (s), 1484 (s), 1359 (m), 1163 (m), 1090 (m),
1012 (m), 952 (m), 859 (m).
GOF
Acknowledgements
We are grateful to the National Natural Science Foundation of
China (Grant Nos. 20632040, 20972107) for the support of this
work.
4.6. X-ray crystallography of complexes 3, 5 and 6
Crystals of complexes 3, 5 and 6 suitable for X-ray diffraction
study were sealed in a thin-walled glass capillary filled under ar-
gon. Diffraction data were collected on a Rigaku Mercury CCD area
Appendix A. Supplementary data
CCDC 751062, 751063 and 751064 contain the supplementary
crystallographic data for complexes 3, 5 and 6. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Center via http://www.ccdc.cam.ac.uk/data_request/cif. Supple-
mentary data associated with this article can be found, in the on-
line version, at doi:10.1016/j.jorganchem.2009.12.010.
detector in
x scan mode using Mo Ka radiation (k = 0.71070 Å).
The diffracted intensities were corrected for Lorentz polarization
effects and empirical absorption corrections. Details of the inten-
sity 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
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.
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