Syntheses and crystal structures of four-coordinate aryloxo neodymium complexes

Article abstract of DOI:10.1016/S0277-5387(00)00535-0

Two four-coordinate complexes of neodymium with 2,6-di-tert-butyl-4-methylphenolate have been synthesized and their single-crystal structures determined. Anhydrous NdCl₃ reacted with ArONa in a 1:3 molar ratio in THF at room temperature to yield the neutral four-coordinate complex [(ArO)₃Nd(THF)]·MePh (1), which crystallized as a solvate, in which three aryloxide ligands and one THF ligand are coordinated to neodymium to form a slightly distorted tetrahedron. The reaction of NdCl₃ with 4 equiv. of ArONa in THF gave [(ArO)₄Nd][Na(THF)₆] (2). In this anion-cation pair compound, the neodymium and sodium atoms exhibit distorted tetrahedral and distorted octahedral coordination geometry, respectively. The average Nd-O(Ar) distance is 2.176 and 2.230 A? in complex 1 and 2, respectively.

Full text of DOI:10.1016/S0277-5387(00)00535-0

www.elsevier.nl/locate/poly
Polyhedron 19 (2000) 2243–2247
Syntheses and crystal structures of four-coordinate aryloxo
neodymium complexes
Li-Lu Zhang a, Ying-Ming Yao a, Yun-Jie Luo a, Qi Shen a,b,*, Jie Sun b
a Department of Chemistry, Suzhou Uni6ersity, Suzhou 215006, People’s Republic of China
b Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China
Received 1 March 2000; accepted 8 August 2000
Abstract
Two four-coordinate complexes of neodymium with 2,6-di-tert-butyl-4-methylphenolate have been synthesized and their
single-crystal structures determined. Anhydrous NdCl3 reacted with ArONa in a 1:3 molar ratio in THF at room temperature to
yield the neutral four-coordinate complex [(ArO)3Nd(THF)]·MePh (1), which crystallized as a solvate, in which three aryloxide
ligands and one THF ligand are coordinated to neodymium to form a slightly distorted tetrahedron. The reaction of NdCl3 with
4 equiv. of ArONa in THF gave [(ArO)4Nd][Na(THF)6] (2). In this anion–cation pair compound, the neodymium and sodium
atoms exhibit distorted tetrahedral and distorted octahedral coordination geometry, respectively. The average NdꢀO(Ar) distance
,
is 2.176 and 2.230 A in complex 1 and 2, respectively. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Synthesis; Crystal structure; Aryloxide; Neodymium; Anion–cation pair compound
used as ligands [11–13]. However, for a less bulky
1. Introduction
ligand, such as 2,6-diisopropyl phenoxide, anionic ate
complexes containing alkali metals are obtained via
bridging interactions to form one-dimensional chains,
two-dimensional sheets or extended three-dimensional
structures [14,15]. Recently, homoleptic anionic arylox-
ide–lanthanoid complexes have also been obtained by
Clark and Deacon et al. using substituted phenoxides
as ligands [16–18].
Previous studies with the 2,6-di-tert-butyl-4-methyl
phenoxo ligand, O-C6H2-2,6-tert-Bu-4-Me, (OAr in
this paper) have shown that it gives low-coordinate
neutral monomeric complexes with scandium and sa-
marium, Sc(ArO)3 and [Sm(ArO)3(THF)]·THF, from
the reaction of LnCl3 with NaOAr [11,19]. To under-
stand more about this reaction with the other lan-
thanide elements, we have studied the reaction of
anhydrous NdCl3 with 3 and 4 equiv. of NaOAr in
THF, and the desired complex [Nd(ArO)3(THF)]·MePh
(1) and unusual compound [Nd(ArO)4][Na(THF)6] (2)
were synthesized. Single-crystal structure studies re-
vealed that the latter is a disconnected anion–cation
pair compound with the sodium well separated from
the lanthanoid coordination sphere.
Lanthanide alkoxides and aryloxides have found a
variety of applications as homogeneous catalysts for
organic reactions [1] and precursors for organolan-
thanide syntheses [2] and high purity oxide materials
[3]. The syntheses, structures and reactivities of alkoxo-
and aryloxolanthanide complexes have recently at-
tracted a great deal of attention [4–6]. Investigation
into the chemistry of lanthanide complexes containing
aryloxo ligands has produced complexes exhibiting a
variety of structural types [7–9]. The coordination
number and degree of oligomerization of the products
can be controlled by varying the bulky substituents on
the arene ring in the reaction of europium ingot with
substituted phenols [9,10]. These facts are consistent
with general expectations. From metathesis reactions,
the neutral monomeric or dimeric complexes can be
obtained when the bulky substituted phenoxides are
* Corresponding author. Tel.: +86-512-511-2513; fax: +86-512-
511-2371.
E-mail address: qshen@suda.edu.cn (Q. Shen).
0277-5387/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S0277-5387(00)00535-0

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L.-L. Zhang et al. / Polyhedron 19 (2000) 2243–2247
2. Experimental
at −20°C for crystallization. Blue single crystals suit-
able for X-ray determination were obtained over a few
days (yield 3.15 g, 72%). Found: Nd, 14.83. Calc. for
[Nd(ArO)3(THF)]·(MePh): Nd, 14.92%. IR absorptions
(cm−1): 2957(s), 2918(w), 2873(w), 1634(s), 1434(s),
1396(m), 1362(m), 1231(m), 1151(s), 1065(m), 1027(w),
864(s), 771(s), 460(m).
All manipulations were performed under argon using
the Schlenk technique. THF was distilled from sodium
benzophenone ketyl before use. Anhydrous NdCl3 was
prepared according to the literature method [20].
NaOAr was prepared from the reaction of ArOH and
Na in THF. Metal analyses were carried out using
complexometric titration [21]. IR spectra were recorded
2.2. Synthesis of [Nd(ArO)4][Na(THF)6] (2)
1
on a Nicolet-550 FTIR spectrometer as KBr pellets. H
and 13C NMR spectra were recorded on a Bruker
AM-300 spectrometer in C6D6.
A solution of NaOAr (25.0 cm3, 21.56 mmol) in THF
was slowly added to a suspension of NdCl3 (1.352 g,
5.39 mmol) in 25 cm3 THF at room temperature. After
stirring for 72 h, the precipitate was removed from the
reaction mixture by centrifugation. The solvent was
removed in vacuum and toluene was added. The precip-
itate was separated and the solution concentrated, and
then cooled at −20°C. The yellow crystals were ob-
tained after several weeks (4.05 g, 51%). Found: Nd,
9.62. Calc. for [Nd(ArO)4][Na(THF)6]: 9.75%. IR ab-
sorptions (cm−1): 2962(s), 2925(m), 2876(w), 1637(s),
1437(s), 1225(s), 1159(s), 864(m), 771(m), 507(s). 1H
NMR (C6D6): l 7.16(8H, Ph), 2.35(12H, Me), 1.62
(48H, THF), −1.11(72H, But). 13C NMR: 123.3(PhO),
88.7(PhO), 84.2(PhO), 74.9 (PhO), −9.3(THF),
−19.8(Me), −26.8(THF), −28.9(Me), −29.4(But),
−29.6(But).
2.1. Synthesis of [Nd(ArO)3(THF)]·MePh (1)
A solution of NaOAr (15.7 cm3, 13.59 mmol) in THF
was slowly added to a suspension of NdCl3 (1.135 g,
4.53 mmol) in 20 cm3 THF at room temperature. After
being stirred for 72 h, the NaCl was separated from the
reaction mixture by centrifugation. The solvent was
removed in vacuum and toluene was added to extract
the product. The dissolved portion was removed by
centrifugation. The filtrate was concentrated and cooled
Table 1
Crystal data and experimental parameters
2.3. Crystallography
Compound
[Nd(OAr)3(THF)]· [Nd(OAr)4]-
MePh (1)
[Na(THF)6] (2)
Single crystals suitable for X-ray measurements were
sealed in thin-walled glass capillaries under argon. In-
tensity data were collected in the variable ꢀ scan mode
on a Rigaku AFC 7R four-circle diffractometer using
Formula
C56H85NdO4
966.48
0.20×0.20×0.30
monoclinic
blue, prism
Cc (No. 9)
C84H140O10NaNd
1477.26
0.20×0.25×0.30
monoclinic
yellow, prism
P21/c (No. 14)
Molecular weight
Crystal size (mm)
Crystal system
Crystal color and habit
Space group
,
Mo Ka radiation (u=0.71073 A) at 293 K. Crystallo-
graphic data are listed in Table 1.
The crystal structures of complexes 1 and 2 were
determined by direct methods which yielded the posi-
tions of all non-hydrogen atoms. All the non-hydrogen
atoms were refined anisotropically. Hydrogen atoms
were all generated geometrically (CꢀH bond lengths
Unit cell dimensions
,
a (A)
25.907(1)
10.601(1)
20.160(1)
103.38(1)
5386.5(6)
1.192
14.414(2)
15.119(2)
39.686(4)
97.28(2)
8579(4)
1.144
4
0.661
3180
293
,
b (A)
,
c (A)
i (°)
3
,
V (A )
,
fixed at 0.96 A), assigned appropriate isotropic thermal
Dcalc (g cm−3
)
parameters and allowed to ride on their parent carbon
atoms. All the H atoms were held stationary and were
included in the structure factor calculation in the final
stage of full-matrix least-squares refinement.
Z
4
v (mm−1
F(000)
)
1.005
2052
293(2)
ꢀ
Temperature (K)
Scan type
ꢀ
qmax (°)
Number of unique
reflections
24.99
3827
22.46
9139
3. Results and discussion
Number of reflections with 3819
I]2.0|(I)
6039
637
3.1. Syntheses of the complexes
Number of parameters
550
refined
The metathesis reaction between anhydrous NdCl3
and NaOAr in the molar ratio 1:3 in THF at room
temperature, followed by crystallization from toluene,
yielded the neutral four-coordinate neodymium com-
R
0.0397
0.1023
0.965
0.0640
0.0840
2.93
Rw
Goodness-of-fit

L.-L. Zhang et al. / Polyhedron 19 (2000) 2243–2247
2245
Table 2
unusual compound [Nd(ArO)4][Na(THF)6] as illus-
trated in Eq. (3).
,
Selected bond lengths (A) and angles (°) in compound 1 and 2
NdCl3+4NaOART“HF[(ArO)4Nd][Na(THF)6]+3NaCl
[Nd(OAr)3(THF)]·MePh (1)
Nd(1)ꢀO(1)
Nd(1)ꢀO(3)
O(1)ꢀC(1)
O(3)ꢀC(31)
O(4)ꢀC(49)
2.173(5)
2.164(5)
1.367(8)
1.370(9)
1.452(11)
Nd(1)ꢀO(2)
Nd(1)ꢀO(4)
O(2)ꢀC(16)
O(4)ꢀC(46)
2.190(5)
2.444(6)
1.356(8)
1.450(12)
(3)
1H, 13C NMR and IR studies show that there are not
only phenolate ligand signals, but also THF signals. A
single-crystal study reveals (see below) that compound
2 contains a discrete homoleptic aryloxoneodymium
anion with the alkali metal cation well separated from
the neodymium coordination sphere. To our knowl-
edge, only three analogous complexes [Na(diglyme)2]-
O(1)ꢀNd(1)ꢀO(2) 115.5(2)
O(1)ꢀNd(1)ꢀO(4) 100.8(2)
O(2)ꢀNd(1)ꢀO(4) 107.7(2)
Nd(1)ꢀO(1)ꢀC(1) 162.0(5)
Nd(1)ꢀO(3)ꢀC(31) 155.9(5)
Nd(1)ꢀO(4)ꢀC(49) 130.5(5)
O(1)ꢀNd(1)ꢀO(3) 119.7(2)
O(2)ꢀNd(1)ꢀO(3) 116.5(2)
O(3)ꢀNd(1)ꢀO(4)
Nd(1)ꢀO(2)ꢀC(16) 147.3(4)
Nd(1)ꢀO(4)ꢀC(46) 120.2(5)
90.7(2)
[Nd(Odpp)4],
[Odpp=2,6-diphenylphenolate,
di-
[Nd(OAr)4][Na(THF)6] (2)
NdꢀO(1)
NdꢀO(3)
NaꢀO(5)
NaꢀO(7)
NaꢀO(9)
O(1)ꢀC(1)
O(3)ꢀC(31)
2.202(6)
2.247(7)
2.33(2)
2.36(1)
2.33(2)
1.36(1)
1.35(1)
NdꢀO(2)
NdꢀO(4)
NaꢀO(6)
2.256(7)
glyme=bis(2-methoxyethyl) ether], [Na(diglyme)2]-
[Er(Odpp)4] and [Na(DME)2][Nd(Odpp)4] (DME=1,2-
dimethoxyethane) have been recently reported in the
literature [18]. Generally, unidentate coordinating or
non-coordinating solvents were considered disadvanta-
geous for ion pair complex formation. Watkin et al.
reported that Sm(OC6H3ꢀPr2i-2,6)3(THF)2 reacted with
one equiv. of LiC5Me5 in THF to form the lithium ate
complex, which however reacted with an excess of
2.217(7)
2.49(2)
2.32(2)
2.36(1)
1.34(1)
1.36(1)
NaꢀO(8)
NaꢀO(10)
O(2)ꢀC(16)
O(4)ꢀC(46)
O(1)ꢀNdꢀO(2)
O(1)ꢀNdꢀO(4)
O(2)ꢀNdꢀO(4)
O(5)ꢀNaꢀO(6)
O(5)ꢀNaꢀO(8)
O(5)ꢀNaꢀO(10)
O(6)ꢀNaꢀO(8)
O(6)ꢀNaꢀO(10)
O(7)ꢀNaꢀO(9)
O(8)ꢀNaꢀO(9)
O(9)ꢀNaꢀO(10)
108.2(2)
104.3(2)
111.5(3)
88.7(7)
173.0(9)
93.7(7)
88.8(7)
97.4(6)
87.0(5)
91.4(9)
89.0(5)
O(1)ꢀNdꢀO(3)
O(2)ꢀNdꢀO(3)
O(3)ꢀNdꢀO(4)
O(5)ꢀNaꢀO(7)
O(5)ꢀNaꢀO(9)
O(6)ꢀNaꢀO(7)
O(6)ꢀNaꢀO(9)
O(7)ꢀNaꢀO(8)
O(7)ꢀNaꢀO(10)
O(8)ꢀNaꢀO(10)
112.7(2)
110.8(2)
109.1(2)
89.8(8)
90.4(8)
86.7(6)
173.6(7)
83.6(7)
174.7(5)
93.1(7)
TMEDA (tetramethylethylenediamine) to form
a
charge–separated salt [22]. In our case, the discon-
nected anion–cation pair compound can be crystallized
from mixed THF–toluene solvent. This difference may
be attributed to the large size of the substituents on the
arene ring.
3.2. Structures
The molecular structures of compound 1 and 2 were
determined by single-crystal studies. The selected bond
lengths and angles are listed in Table 2.
plex [Nd(ArO)3(THF)]·MePh in high yield, as shown in
Eq. (1).
NdCl3+3NaOArT“HF(ArO)3Nd(THF)+3NaCl
(1)
3.2.1. Crystal structure of [Nd(OAr)3(THF)]·MePh (1)
The molecular structure of [Nd(OAr)3(THF)]·MePh
is shown in Fig. 1. The compound is isostructural with
[Sm(OAr)3(THF)]·THF and the toluene solvent
molecule replaces the THF molecule in the molecular
This reaction is similar to the reaction of NaOAr
with anhydrous SmCl3 [19], but different from that of
2,6-diisopropylphenoxide which reacted with NdCl3 in
THF to produce K[Nd(OC6H3-Pr2i-2,6)4] instead of
Nd(OC6H3ꢀPr2i-2,6)3 [14]. Subsequent studies have
shown that LnCl3 reacted with 4 equiv. of potassium
2,6-diisopropylphenoxide in THF, followed by crystal-
lization from toluene, to form the ‘ate’ complex
K[Ln(OC6H3ꢀPr2i-2,6)4] in high yield as shown in Eq.
(2) [15].
packing [19]. The complex is
a four-coordinate
monomer with three aryloxo oxygen atoms and one
THF oxygen atom around the neodymium forming a
distorted tetrahedron. The coordination geometry
around the metal is different from that in
[Nd(Odpp)3(THF)] which has a distorted trigonal
bipyramidal array by forming an intramolecular p-
bond [23]. Interestingly, in [Nd(Odpp)3(DME)] [24],
1. THF
“
LnCl3+4KꢀOC6H3ꢀPri2-2,6
[Nd(Odpp)3(THF)2],
[Nd(Odpp)3(THF)]
and
2. Toluene
K[Ln(OC6H3ꢀPri2-2,6)4+3KCL
(2)
Nd(Odpp)3 [23], all of these compounds show distorted
trigonal bipyramidal stereochemistry and the
neodymium atoms are five- or seven-coordinate. Few
examples of four-coordinate neodymium complexes are
known. Evans and co-workers reported the structure of
The reaction of anhydrous NdCl3 with 4 equiv. of
NaOAr in THF at room temperature, did not give the
‘ate’ complex Na[Nd(OAr)4], but rather produced the

2246
L.-L. Zhang et al. / Polyhedron 19 (2000) 2243–2247
,
those for [Sm(OAr)3(THF)]·THF (1.31 A) [19], and
,
Sc(OAr)3 (1.30 A) [8], but a little longer than those for
other aryloxo lanthanide complexes [Yb(Odpp)3-
,
,
(THF)2] (1.27 A) [27] [La(Odpp)3(THF)2] (1.28 A) [28],
t
,
and Yb(OC6H2Bu3-2,4,6)3(THF) (1.27 A) [29]. The
,
NdꢀO(THF) distance is 2.444(6) A, and a similar sub-
traction from this value gives 1.58 A. This is much
higher than the usual value 1.34 A for organolan-
,
,
thanoid complexes [30], but still within the range for
the complexes of bulky lanthanoid aryloxides
[19,27,29].
3.2.2. Crystal structure of [Nd(OAr)4][Na(THF)6] (2)
The molecular structure of 2 is comprised of a dis-
crete [Na(THF)6]+ cation and a [Nd(ArO)4]− anion
(Fig. 2).
In the anion, the neodymium metal is coordinated to
four oxygen atoms from aryloxide ligands in a pseudo-
tetrahedral fashion. The stereochemistry around the
Fig. 1. Molecular structure of [Nd(ArO)3(THF)]·(MePh).
a four-coordinate neodymium amide complex; however,
to achieve steric saturation of the metal center, an
neodymium
atom
is
similar
to
that
in
K[Nd(OC6H3ꢀPr2i-2,6)[15], [Na(diglyme)2][Nd(Odpp)4]
and [Na(diglyme)2][Er(Odpp)4] [18]. The NdꢀO dis-
agostic interaction between the
a
carbon and
neodymium was observed [25]. The current difference in
the coordination number can be attributed to the more
bulky ArO ligand as compared to the Odpp ligand and
amide.
,
tances range from 2.202(6) to 2.256(7) A, giving the
average distance of 2.230 A, which is somewhat longer
than the average NdꢀO(Ar) distance (2.176 A) observed
,
,
for complex 1, although both of them have similar
stereochemical arrangement around the central metal.
This difference can be attributed to steric repulsion, as
an additional ArO ligand replacing the THF ligand
increases the steric repulsion among the ligands. It is
also longer than that in the analogous aryloxide com-
plex [Na(diglyme)2][Nd(Odpp)4] [18], which is consis-
tent with the fact that ArO is more bulky than Odpp.
The NdꢀO(Ar) distances in complex 2 are similar
to those in K[Nd(OC6H3Pr2i-2,6)4] (average=2.21
The three aryloxo oxygen atoms around neodymium
show a nearly trigonal planar array with S OꢀNdꢀO=
351.7°; this value is comparable with those in
Nd(Odpp)3(THF) (358.7°) and Nd(Odpp)3 (353.2°) [23].
The NdꢀO(Ar) distances range from 2.164(5) to
,
2.190(5) A, giving the average NdꢀO(Ar) distance 2.176
,
A. This value is a little shorter than those in
,
[Nd(Odpp)3(DME)] (2.191 A) [24], [Nd(Odpp)3(THF)2]
,
,
(2.190 A), [Nd(Odpp)3(THF)] (2.193 A) [23],
i
,
K[Nd(OC6H3ꢀPr2-2,6) (2.211 A) [15] and comparable
with that in Nd(Odpp)3 (2.169 A) [23]. Subtraction of
,
,
A) [14] and Na[Nd(Odpp)4] (2.20 A) [17,18], but
slightly longer than those in [Nd(Odpp)3](THF) (2.193
,
,
,
,
the estimated radius (0.86 A) [26] for four-coordinate
A) and Nd(Odpp)3 (2.169 A) [23]. The NdꢀO dis-
Nd3+ from NdꢀO(Ar) gives 1.31 A, which is similar to
tance is also longer than the ErꢀO(Ar) distance in
,
Fig. 2. Molecular structure of [Nd(ArO)4][Na(THF)6].

L.-L. Zhang et al. / Polyhedron 19 (2000) 2243–2247
2247
[Na(diglyme)2][Er(Odpp)4] even if the differences in ionic
radii are considered [18]. This NdꢀO(Ar) distance is very
istry, The Chinese University of Hong Kong, for carrying
out the X-ray structure determination.
,
similar to ŽNdꢀObr (2.211 A) and apparently longer
i
,
than ŽNdꢀOter (2.122 A) of Nd2(O-2,3- Pr2C6H3)6 [7].
References
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1.34(1) to 1.36(1) A, and are apparently shorter than the
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,
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,
bond length is 1.35 A, and is similar to that in complex
t
,
,
1 (1.36 A), Yb(OC6H2Bu3-2,4,6)3(THF) (1.38 A) [29],
,
[Yb(Odpp)3(THF)2] (1.33 A) [27], and [La(Odpp)3-
(THF)2] (1.31 A) [28].
,
The six OꢀNdꢀO angles range from 104.3(2) to
112.7(2)°, which is comparable with those angles in
[Na(diglyme)2][Nd(Odpp)4] [18]. But there are apparently
differences from those in K[(Nd(O-2,6-Pr2iC6H3)4] [14], in
which one of the six OꢀNdꢀO angles (95.29°) deviates
significantly from that of an ideal tetrahedron because of
the interaction between the potassium atom and two
aryloxide ligands. The NdꢀOꢀC angles range from
144.6(7) to 167.9(7)°.
In the cation [Na(THF)6]+, the sodium ion is solvated
and octahedrally bonded to the oxygen atoms of six THF
molecules. The bond lengths of NaꢀO range from 2.32(2)
,
to 2.49(2) A and the angles for the two closest oxygen
atoms to the sodium range from 83.6(7) to 97.4(6)°. These
are slightly different from the values 2.380(5)–2.434(4),
,
2.340(10)–2.4410(10) A and 88.2(2)–92.8(2), 88.8(4)–
91.2(4)° in [Na(THF)6][(C9H7)3Nd(m-Cl)Nd(C9H7)3] [31]
and [Na(THF)6][Cp3Lu(m-H)LuCp3] [32], respectively.
Actually, in the last two compounds, the cations are
centrosymmetrical, but in complex 2, the O(5)ꢀNaꢀO(8),
O(6)ꢀNaꢀO(9) and O(7)ꢀNaꢀO(10) angles are 173.0(9),
173.6(7) and 174.7(5)°, respectively. These values show
the cation is a distorted octahedron.
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4. Supplementary data
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC No. 136299 for compound 1 and
CCDC No. 136300 for compound 2. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ,
UK (fax: +44-1223-336033; e-mail:deposit@ccdc.cam.
ac.uk or www:http://www.ccdc.cam.ac.uk).
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Acknowledgements
This work was supported by State Project for Basic
Research, Chinese National Natural Science Foundation
and the Key Laboratory of Organic Synthesis of Jiangsu
Province. Thanks are due to the Department of Chem-
.