Polyhedron 83 (2014) 236241

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Iron(II) complexes bearing anilido-imine ligands: Synthesis and catalysis on ATRP

of methyl methacrylate

Zhiqiang Hao, Yuxi Han, Wei Gao , Lan Xin, Ying Mu
State Key Laboratory for Supramolecular Structure and Materials, School of Chemistry, Jilin University, Changchun 130012, China
article info abstract
n
Article history: Reactions of the ortho-C6H4(NHAr)-(CH@NAr) with BuLi and subsequent addition of FeCl 2 afford the ani-lido-aldimine
Received 15 April 2014 Fe(II) complexes [(ArN@CHC6H4-NAr)Fe]2(l-Cl)2 (Ar = 2,6-Me2C6H3 (1a); Ar = 2,6-Et2C6H3 (1b)), and (ArN@CHC6H4-
Accepted 2 August 2014 Available i n
online 12 August 2014
NAr)Fe(l-Cl)2Li(THF)2 (Ar = 2,6- Pr2C6H3 (1c)). Similarly, reactions of the 2-(ArNC(H))C6H4-HNC9H6N with BuLi and
FeCl2 give the N,N,N-tridentate iron complexes {[2-(ArNC(H))C 6H4-NC9H6N]Fe}2(l-Cl)2 (Ar = 2,6-Me 2C6H3 (2a), 2,6-
i
Keywords: Et2C6H3 (2b), and 2,6- Pr2C6H3 (2c)). The X-ray diffraction analysis reveals that 1a and 1b are dimeric complexes and 1c is
Iron complexes MMA hetero-binuclear complex. Fe(II) atoms in these complexes are all in a distorted tetrahedral geometry. Complex 2c was
polymerization confirmed to be a dimeric complex with the iron atom in a trigonal bipyramidal geometry. Complexes 1a1c show moderate
ATRP activities in ATRP of MMA in the presence of benzyl chloride (BnCl). While complexes 2a2c are inert under the same
Anilido-imine ligands condition.
Controlled polymerization
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Atom transfer radical polymerization (ATRP), using metal-med-iated
halogen exchange to control the equilibrium between active and dormant
polymer chains, has attracted considerable attentions and was widely used as
an important methodology to construct well defined polymers in laboratory
and industry [1]. Since its first discovery in 1995, ATRP has become a power
tool for preparing new polymers with controlled molecular weights and well-
defined microstructures. So far, many kinds of metal complexes such as
copper [1c,1e,1h,2], nickel [3], ruthenium [1b,4], and other metals [5] have
been tested as pre-catalyst for ATRP, in which the iron complexes have
attracted more and more attention due to their low toxicity, low cost, good
biocompatibility and potential applica-tion in biomaterials [6]. Generally,
some ligands were added to these systems to improve the solubility of the
metal species in the solution. And it is well also established that the ligands in
the complexes play an important role in the catalytic performance, because a
suitable ligand can lower the redox potential of the metal and improve both
the activity and the controllability of the catalysts [1]. In recent years many
works have focus on the inves-tigation on iron complexes in (R)ATRP.
Various ligands such as poly-dentate amines [7], phosphines [8], imines [9],
carbenes
Corresponding authors. Tel./fax: +86 431 85168376.
E-mail addresses: gw@jlu.edu.cn (W. Gao), ymu@jlu.edu.cn (Y. Mu).
http://dx.doi.org/10.1016/j.poly.2014.08.003 0277-5387/
2014 Elsevier Ltd. All rights reserved.
[10], organic acids [11], and thiocarbamates [12] was investigated to support
iron complexes, in which the poly-dentate nitrogen ligands have drawn
especial attention. For example, the Fe(II) com-plexes bearing diimine or N-
alkyl-2-pyridylmethanimine ligands [13] show high efficiency and good
controllability in ATRP of sty-rene and MMA respectively. Some tetradentate
N,N,N,N ligands, such as dichloro{[N,N 0-diphenyl-N,N0-di(quinoline-2-
methyl)]-1, 2-ethylene-diamine}, {[N,N0-dioctyl-N,N0-di(quinoline-2-
methyl)]-1,2-ethylene diamine}, {[N,N0-dibenzyl-N,N0-di(quinoline-2-
methyl)]-1,2-ethylene diamine}, and (1R,2R)-(-)-N,N0-di(quinoline-2-
methyl) diiminocyclohexane, in combination with Fe(II), were proved to be
efficient catalysts for ATRP of methyl methacrylate, in which conversions of
8743% were obtained in 3090 min [14].
Recently, our interest has been focused on the anilido-imine ligands and
the quinolinyl anilido-imine ligands. These ligands fea-ture easy preparation
and fine-tuning of the steric and electronic properties at the metal centers and
have been investigated in sup-porting main group complexes, transition metal
complexes, and rare-earth metal complexes [15]. The anilido-imine nickel
com-plexes show moderate activities in olefin polymerization. The quinolinyl
anilido-imine rare-earth-metal complexes, aluminum and zinc complexes, and
nickel complexes show high activity and good molecular weight
controllability in e-caprolactone polymeri-zation, lactide ring-opening
polymerization, and norbornene poly-merization respectively [16].
In this
paper, we report the synthesis and characterization of several
iron(II) complexes supported by
Z. Hao et al. / Polyhedron 83 (2014) 236241 237

anilido-imine ligands and quinolinyl anilido-imine ligands. The catalytic
behavior of these iron(II) complexes towards the ATRP of MMA were also
presented (see Scheme 1).
2. Experimental
2.1. General procedures and methods
All manipulations involving air and moisture-sensitive com-pounds were
carried out under an atmosphere of dried and puri-fied nitrogen using standard
Schlenk or dry box techniques. Toluene and hexane were dried over
sodium/benzophenone and distilled under nitrogen prior to use. Elemental
analyses were per-formed on a Varian EL miFeoanalyzer. NMR spectra were
recorded on a Varian Mercury-300 NMR spectrometer at room temperature in
CDCl3 or C6D6. The molecular weight and molecular weight dis-tribution of
the polymers were measured on a TOSOH HLC 8220 GPC at 40 LC using
THF as eluent at a flow rate of 1.0 mL/min. Polystyrene standards were used
for calibrations. The ligands were synthesized according to literature
procedures [15a,16c].
2.2. Iron complexes preparation and characterization
2.2.1. Preparation of complex 1a
n
Under a nitrogen atmosphere, BuLi (2.00 M in hexane, 0.50 mL, 1.00
mmol) was added dropwise to ortho-C 6H4(NH-2,6-Me2C6H3)-(CH@N-2,6-
Me2C6H3) (0.33 g, 1.00 mmol) in 25 mL THF at 78 LC. After stirred for 1 h,
the reaction mixture was warmed to 40 LC and then FeCl 2 (0.13 g, 1.00
mmol) was added in one portion. The reaction mixture was allowed to warm
to room temperature gradually and stirred over night. Removal of volatiles in
vacuum and crystallization of the residue with toluene afford complex 1a as
red powders (0.37 g, 87.8%). Single crystals for X-ray analysis were grew
from THF/hexane at 30 LC within several days as red blocks. Anal. Calc. for
C46H46Cl2N4Fe2 (%): C, 65.97; H, 5.54; N, 6.69. Found: C, 65.91; H, 5.62;
1
N, 6.72. IR(KBr): m m (cm ) 1657m, 1600m, 1539s, 1491m, 1455vs, 1369s,
1321m, 1294w, 1172w, 1161s, 812m, 744m (see Scheme 2).
2.2.2. Preparation of complex 1b
Following the same procedure described for 1a, treatment of ortho-
C6H4(NH-2,6-Et2C6H3)-(CH@N-2,6-Et2C6H3) (0.39 g, 1.00 mmol in 25 mL
n 3738m, 3625m, 1730m, 1643s, 1563s, 1515s, 1452m, 744w, 666w.
THF) with BuLi (2.00 M in hexane, 0.50 mL, 1.00 mmol) and then in situ
addition of FeCl2 (0.13 g, 1.00 mmol) gave 1b in an 85.9% yield (0.41 g).
Red crystals for X-ray analysis were grew from the mixture of toluene and
hexane at 30 LC within several days. Anal. Calc. for C 54H62Cl2N4Fe2: C,
68.29; H, 6.58; N, 5.90. Found: C, 68.42; H, 6.62; N, 5.84. IR(KBr): m m
1
(cm ) 1944w, 1733m, 1705m, 1656m, 1561s,1539s, 1503s, 1372m, 1147m,
819w, 414m.
2.2.3. Preparation of complex 1c
Following the same procedure described for 1a, treatment of ortho-
i
C6H4(NH-2,6-Et2C6H3)-(CH@N-2,6- Pr2C6H3) (0.44 g, 1.00
n
mmol) with BuLi (2.00 M in hexane, 0.50 mL, 1.00 mmol) and then in situ
addition of FeCl2 (0.13 g, 1.00 mmol) afford 1c as red pow-der (0.65 g,
90.4%). Red crystals for X-ray analysis were grew from the mixture of THF
and hexane at 30 LC within several days. Anal. Calc. for
C39H55Cl2FeLiN2O2: C, 65.28; H, 7.73; N, 3.90. Found: C, 64.97; H, 7.68; N,
1
3.98. IR(KBr): m m (cm ) 3868w, 3743w, 3629w, 1640m, 1557s, 1457s,
1390s, 1154m, 751m.
2.2.4. Preparation of complex 2a
n
Under a nitrogen atmosphere, BuLi (2.00 M in hexane, 0.50 mL, 1.00
mmol) was added dropwise to a THF solution (25 mL) of 2-(2,6-
Me2C6H3NC(H))C6H4-HNC9H6N (0.35 g, 1.00 mmol) at 78 LC. The reaction
solution was warmed to 40 LC and then the FeCl 2 (0.13 g, 1.00 mmol) was
added. The reaction mixture was allowed to warm to room temperature
gradually and stirred overnight. Removal of volatiles under reduced pressure
and crys-tallization of the residue with toluene afford complex 2a as red
powders (0.39 g, 86.4%). Anal. Calc. for C48H40Cl2N6Fe2 (%): C, 65.26; H,
1
4.56; N, 9.51. Found: C, 65.54; H, 4.62; N, 9.38. IR(KBr): m m (cm ) 3851m,
3674m, 3626m, 1771w, 1735m, 1692s, 1647s, 1555s, 1507s, 1457m, 1423w,
1337w, 766w.
2.2.5. Preparation of complex 2b
Following the same procedure described for 2a, treatment of 2-(2,6-
Et2C6H3NC(H))C6H4-HNC9H6N (0.38 g, 1.00 mmol in 25 mL THF) with
n
BuLi (2.00 M in hexane, 0.50 mL, 1.00 mmol) and then in situ addition of
FeCl2 (0.13 g, 1.00 mmol) give 2b in an 84.7% yield (0.40 g). Anal. Calc. for
C52H48Cl2N6Fe2: C, 66.47; H, 5.15; N, 8.94. Found: C, 66.34; H, 5.32; N,
1
8.85. IR(KBr): m m (cm ) 3852w, 3628w, 3563w, 1648m, 1623s, 1508s,
1453s, 1177w, 745m.
2.2.6. Preparation of complex 2c
Following the same procedure described for 2a, treatment of 2-(2,6-
i
Pr2C6H3NC(H))C6H4-HNC9H6N (0.41 g, 1.00 mmol in 25 mL THF) with
n
BuLi (2.00 M in hexane, 0.50 mL, 1.00 mmol) and then in situ addition of
FeCl2 (0.13 g, 1.00 mmol) afford 2c in an 89.5% yield (0.45 g). Red crystals
for X-ray analysis were grew from the mixture of toluene and hexane at 30
LC within several days. Anal. Calc. for C 56H56Cl2N6Fe2: C, 67.55; H, 5.67;
1
N, 8.44. Found: C, 67.75; H, 5.84; N, 8.25. IR(KBr): m m (cm ) 3854m,
2.3. Polymerizations
A glass tube was loaded with the catalyst and then correspond-ing
equivalent of MMA, initiator and toluene were added in sequence. The tube
was sealed under argon and placed in an oil bath thermostated at the desired
temperature. After desired period of time the reaction mixture was poured into
50 mL of ethanol. The polymer was isolated by filtration, washed with ethanol
and dried under vacuum at 40 LC for 12 h.
 Ar Ar Ar Ar Ar
N n NH N N Cl O
N Cl BuLi THF nBuLi THF
Fe Fe Fe Li
Cl
N Cl N FeCl2 FeCl2 N O
Ar Ar Ar
i
1a, Ar = 2,6-Me2C6H3; 1c, Ar = 2,6- Pr2C6H3
1b, Ar = 2,6-Et C H
2 6 3
Scheme 1. Synthesis of anilido-imino Fe(II) complexes.
238 Z. Hao et al. / Polyhedron 83 (2014) 236241
 N Cl Ar
N
N
NH n
1. BuLi Fe Cl Fe N
N 2. FeCl2 N N
N Ar Ar

2a, Ar = 2,6-Me2C6H3
2b, Ar = 2,6-Et2C6H3
2c, Ar = 2,6-iPr2C6H3
 Scheme 2. Synthesis of quinolinyl anilido-imino Fe(II) complexes.

2.4. Crystal structure determination


The crystals were mounted on a
glass fiber using the oil drop. Data
obtained with the x 2h scan mode
were collected on a Bruker SMART
1000 CCD diffractometer with
graphite-monochro-mated Mo Ka
radiation (k = 0.71073 ). The
structures were solved by direct
methods, and refined with full-
2 in 1a and 0.0942 (av) in 1b. The
matrix least squares on F . All non-
hydrogen atoms were refined
anisotropically and hydro-gen
atoms were introduced in calculated
positions with the dis-placement
factors of the host carbon atoms. All
calculations were performed using
the SHELXT crystallographic
software packages. In complex 1c,
the two THF molecules attached to
the lithium atom are disordered and
one disordered THF was resolved
but the other one is difficult to be
resolved. In complex 2c, there is a
toluene molecule disordered
between two positions. Some large
residual electron densities around
the toluene cannot be well resolved
due to the disorder.
centrosymmetric dimeric with the
Fe(II) atoms in a distorted
tetrahedral environment. The two
anilido- groups and the two imino-
groups in two separate moieties are
arranged in trans-positions
respectively. The iron(II) atoms are
essentially coplanar with the
anilido-imine frameworks with the
average deviations of 0.0913 (av)
two N-aryl rings in the same moiety
are oriented essentially orthogonal
to the parent plane respectively. The
FeCl bond dis-tances of 2.3570
(av) in 1a and 2.3661 (av) in 1b
are similar
Fig. 1. Perspective view of complex 1a with
thermal ellipsoids drawn at 30% probability
level. Hydrogens are omitted for clarity. The
selected bond lengths () and angles (deg.):
Fe(1)N(1) 1.945(2), Fe(1)N(2) 2.008(2),
Fe(2)N(3) 1.949(2), Fe(2)N(4) 2.007(2),
Fe(1)Cl(1) 2.3839(8), Fe(1)Cl(2)
2.3358(8), Fe(2)Cl(1) 2.3204(8), Fe(2)
Cl(2) 2.3879(8); N(1)Fe(1)N(2) 92.41(9),
N(3)Fe(1)N(4) 93.05(9), Cl(1)Fe(1)
Cl(2) 92.34(3), Cl(1)Fe(2)Cl(2) 92.63(3).

3. Results and discussion

3.1. Synthesis and characterization

of the Fe(II) complexes

The lithium salt of anilido-imine

ligands (ortho-C6H4(CH@NAr)
ArNLi Ar = 2,6-Me2C6H3 or 2,6-
Et2C6H3), were prepared in situ by
treating the corresponding ligands
n
with BuLi in THF at low tem-
perature. Reactions of these lithium
salts of anilindo-imine ligands with
FeCl2 afford the blood red solution.
Evaporating the solution to dryness
and extracting of the residue with Fig. 2. Perspective view of complex 1b with
toluene afford the anilido-imine thermal ellipsoids drawn at 30% probability
iron(II) complexes 1a and 1b in level. Hydrogens are omitted for clarity. The
high yields as red powder. selected bond lengths () and angles (deg.):
Fe(1)N(1) 1.954(3), Fe(1)N(2) 2.017(2),
No informative NMR spectra of Fe(1)Cl(1) 2.4044(9), Fe(1)Cl(1A)
2.3337(9), Fe(2)N(3) 1.950(3), Fe(2)N(4)
1a and 1b were obtained due to
2.017(2), Fe(2)Cl(2) 2.3338(10), Fe(2)
their paramagnetic nature. 1a and Cl(2A) 2.3928(9); Cl(1)Fe(1)Cl(1A)
1b were characterized with 89.70(3), N(1)Fe(1)N(2) 91.53(11),
elemental analysis and IR. The Cl(2)Fe(2)Cl(2A) 90.97(3), N(3)Fe(2)
molecular structures of 1a and 1b N(4) 92.21(11).

were further established by X-ray

crystallography and were shown in
Figs. 1 and 2 respectively together
with the selected bond dis-tances
and angles. The crystallographic
data are summarized in Table 1.
There are two independent
molecules in the crystallo-graphic
asymmetric unit of 1b with very
similar geometries, so only one
molecule was presented for clarity.
Both 1a and 1b are chloride-bridged
 Z. Hao et al. / Polyhedron 83 (2014) 236241 239
Table 1

Summary of crystallographic data for complexes 1a, 1b, 1c, and 2c.

1a 1b 1c 2c
Formula C H Cl Fe N
46 46 2 2 4 C54H62Cl2Fe2N4 C39H55Cl2FeLiN2O2 C70H56Cl2Fe2N6
F
w 837.47 949.68 717.54 1163.81
Cryst syst monoclinic monoclinic monoclinic monoclinic
Space group P2(1)/n P2(1)/c P2(1)/c P2(1)/c
a () 17.8732(13) 24.813(3) 12.9493(19) 14.8941(10)
b () 11.9590(8) 12.6191(14) 17.601(3) 12.9028(8)
c () 20.2633(14) 16.5332(18) 18.663(3) 16.1092(11)
a (L) 90 90 90.046(3) 90
b (L) 101.1880(10) 107.888(2) 101.508(3) 91.0300(10)
c (L) 90 90 90.069(3) 90
3 4248.9(5) 4926.5(9) 4168.1(11) 3095.3(4)
V ( )
Z 4 4 4 2
3
Dcalc. (g cm ) 1.309 1.280 1.143 1.249
l (mm 1) 0.845 0.737 0.522 0.600
F(0 0 0) 1744 2000 1528 1208
hmax (L) 25.06 25.13 25.00 26.04
Collected reflections 24,256 22,921 21,369 19,029
Unique reflections 7515 8734 7332 6099
R 0.0422 0.0519 0.0747 0.0414
int

Goodness-of-fit (GOF) 1.033 1.028 0.876 1.034

R1 0.0455 0.0538 0.0551 0.0688
wR2 0.0996 0.1212 0.1220 0.1927
3 0.519 and 0.230 0.705 and 0.313 0.410 and 0.204 1.304 and 0.384
Largest difference peak, hole (e )

to those of 2.4029(10)2.5246(9) for the bridging FeCl bonds in the

iminopyridine iron complexes 9c. The FeNamino bond lengths of 1.945(2)
1.949(2) in 1a and 1.950(3)1.954(3) in 1b are slightly shorter than the
FeNimino bond length of 2.008(2) 2.007(2) in 1a and 2.017(2) in 1b.
Reaction of the lithium salt of the bulky ligand (ortho-
i
C6H4(CH@NAr)ArNLi Ar = 2,6- Pr2C6H3) with FeCl2, followed by similar
work up, gives complex 1c in high yield. The X-ray diffraction analysis
shows that 1c was hetero-binuclear. The Fe(II) atoms is in a distorted
tetrahedral environment and two additional THF ligands complementing the
coordinated sphere of the lithium atom. The Fe(II) atom is essen-tially
coplanar with the parent plane and the two N-aryl rings are oriented basically
orthogonal to the parent plane. The bond lengths of FeCl and FeN are very
similar to those in 1a (1b) respectively.

Reactions of the N,N,N tridentate quinolinyl anilido-imine ligands with

n
BuLi and subsequent addition of the FeCl2, afford the corresponding Fe(II)
complexes 2a2c in high yields. These paramagnetic complexes were well
characterized with elemental analysis and IR, and the molecular structure of
2c was confirmed by X-ray crystallography. The molecular structure of 2c is
shown in Fig. 3 together with the selected bond distances and angles. 2c is a
dimeric complex with the two equal moieties linked by two bridging chloride
atoms. The iron atoms are essentially coplanar with the quinolinyl moieties.
Both the five-coordinated Fe(II) atoms are in distorted trigonal bipyramidal
geometries with one Cl and N amine atom in apical positions, and the other Cl,
Nimine, and Nquinolinyl in basal plane. The chloride bridges are asymmetric
[FeCl(1) 2.4130(11) , FeCl(1A) 2.4600(13) ] and are all slightly longer
than those in bidentate analogues (1a, 1b, and 1c). This may be attributed to
the more crowded situation around the iron center in 2c (see Fig. 4).
3.2. ATRP polymerization of MMA with iron complexes
All the iron complexes were tested as catalysts for ATRP of MMA. The
polymerizations were performed in toluene at 100 LC with 1a1c and 2a2c
as catalysts and BnCl as initiator, and the representative polymerization
results are summarized in Table 1. It is shown that complexes 1a, 1b, and 1c
are active for the poly-merization of MMA in the presence of BnCl. While
2a2c are totally
Fig. 3. Perspective view of complex 1c with thermal ellipsoids drawn at 30% probability level.
Hydrogens are omitted for clarity. The selected bond lengths () and angles (deg.): Fe(1)N(1)
2.011(3), Fe(1)N(2) 1.973(2), Fe(1)Cl(1) 2.3086(11), Fe(1)Cl(2) 2.3088(11), Li(1)Cl(1),
2.346(7), Li(1)Cl(2) 2.378(7); Cl(1)Fe(1)Cl(2) 96.92(4), N(1)Fe(1)N(2) 91.39(10), Cl(1)
Li(1)Cl(2) 94.0(2).
inert in the ATRP of MMA and almost no polymer was obtained under the
similar conditions. 1c and 1b show slightly high activi-ties than that of 1a, and
conversions of 5965.5% were obtained in 10 h. The conversions can be
further improved to 76.6% and 78.6% respectively when prolong the
polymerization time to 20 and 40 h respectively. The molecular weights of the
polymer were slightly higher than the calculated values, indicating the lower
effi-ciency of these catalytic systems presumably caused by the slow
deactivation. The PDIs were also relatively high (>1.5) (Table 2, entries 1, 2,
and 5). In the case of higher amount of BnCl, higher conversion rates were
obtained and the Mn decreased gradually from 33 200 to 8700 when the ratios
of the initiator to monomer increased form 1:1 to 10:1. Dynamic study of the
polymerization with 1c shows that the conversion increased with
polymerization time, which had linear correlation with the number-average
240 Z. Hao et al. / Polyhedron 83 (2014) 236241
 (c) J.S. Wang, K. Matyjaszewski, J.
Am. Chem. Soc. 117 (1995) 5614;
molecular weight (Mn) of the (d) K. Matyjaszewski, N.V. Tsarevsky,
Fig. 5. Polymerization of MMA with
obtained polymer; meanwhile, the Nat. Chem. 1 (2009) 276;
1c/BnCl: molecular weight vs. conversion. (e) K. Kamigaito, T. Ando, M.
molecular weight distribution
Conditions: [M]:[I]:[MMA] = 1:5:1000, Sawamoto, Chem. Rev. 101 (2001)
100 LC. (Mw/Mn) was narrow and remained 3689;
almost unchanged (1.441.56) (Fig. (f) K. Matyjaszewski, J. Xia, Chem.
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(g) M. Ouchi, T. Terashima, M.
polymerization in the 1c/BnCl
Sawamoto, Acc. Chem. Res. 41
catalytic systems. (2008) 1120;
(h) M. Ouchi, T. Terashima, M.
Sawamoto, Chem. Rev. 109
4. Conclusions (2009) 4963.
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Fe(II) complexes 1a1c, and 2a (b) C.R. Becer, R. Hoogenboom, D.
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been synthesized and structurally Rapid. Commun. 28 (2007) 1161;
(c) A. Hoffmann, O. Bienemann, I.
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Macromolecules 30 (1997) 2249.
Fig. 4. Perspective view of complex 2c with linked by two chlorine bridges. All [4] T. Ando, M. Kato, M. Kamigaito, M.
thermal ellipsoids drawn at 30% probability the Fe(II) atoms in 1a, 1b, and 1c are Sawamoto, Macromolecules 29 (1996)
level. Hydrogens and uncoordinated solvent 1070.
were omitted for clarity. The selected bond
in distorted tetrahedral geometries.
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2.031(3), Fe(1)N(2) 2.113(3), Fe(1)N(3) dimeric complex with the Fe(II) Teyssie, R. Jerome, Macromolecules
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for ATRP of MMA in the presence of [6] (a) T. Ando, M. Kamigaito, M.
Sawamoto, Macromolecules 30 (1997)
BnCl. The complexes 1a1c show 4507;
moderate activities affording the (b) M. Teodorescu, S.G. Gaynor, K.
poly-mers with relatively narrow Matyjaszewski, Macromolecules 33
(2000) 2335;
Table 2 PDI. While 2a2c are inert and
Polymerization of MMA with iron(II) almost no polymer was obtained (c) K. Matyjaszewski, M. Wei, J. Xia,
a
complexes. under similar conditions. N.E. McDermott, Macromolecules 30
Entry Iron Time (1997) 8161;
[M]0/[I]0/
(d) X.-P. Chen, K.-Y. Qiu, Chem.
complex [MMA]0 (h) Commun. (2000) 233;
1 1a 1:5:1000 10 (e) Y. Kotani, M. Kamigaito, M.
Acknowledgements Sawamoto, Macromolecules 32
2 1b 1:5:1000 10
(1997) 6877.
3 1c 1:1:1000 10
We thank the National Natural [7] (a) S. Niibayashi, H. Hayakawa, R.-H.
4 1c 1:2:1000 10
Jin, H. Nagashima, Chem. Commun.
5 1c 1:5:1000 10 Science Foundation of China for (2007) 1855;
6 1c 1:10:1000 10 financial support (Nos. 21374035,
7 1c 1:5:1000 20 (b) L. Zhang, Z. Cheng, Y. L, X. Zhu,
8 1c 1:5:1000 40 J1103302). Macromol. Rapid Commun. 30
a
(2009) 543;
Polymerization condition: [M] = 10 lmol based on the Fe(II); I = Benzyl chlo- (c) R. Luo, A. Sen, Macromolecules
ride; T = 100 LC; 2 mL toluene. Appendix A. Supplementary data 41 (2008) 4514;
b Isolated yield.
(d) C. Uchiike, M. Ouchi, T. Ando, M.
c
Mn(exp.) = ([MMA]0/[I]0)MMMA Conv.(%) + M Kamigaito, M. Sawamoto, J. Polym.
CCDC 996441, 996442, 1015182
weights for the monomer and the initiator. Sci., Part A: Polym. Chem. 46 (2008)
d Determined by GPC relative to polystyrene standards. and 996444 contain the sup- 6819.
plementary crystallographic data for
1a, 1b, 1c and 2c. These data can be
obtained free of charge via
http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the
Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336
033; or e-mail:
deposit@ccdc.cam.ac.uk.

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