Polyhedron 69 (2014) 55–60

Contents lists available at ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Bis(3,5-dimethylpyrazole) copper(II) and zinc(II) complexes as efficient

initiators for the ring opening polymerization of e-caprolactone
and D,L-lactide
Divambal Appavoo a, Bernard Omondi a, Ilia A. Guzei a,b, Juanita L. van Wyk a, Orpah Zinyemba a,
James Darkwa a,⇑
a
Department of Chemistry, University of Johannesburg, P.O. Box X524, Auckland Park 2006, South Africa
b
Department of Chemistry, University of Wisconsin–Madison, Madison, WI 53706, USA

a r t i c l e i n f o a b s t r a c t

Article history: 3,5-Dimethylpyrazole (L), reacts with [Cu(OAc)2] or [Zn(OAc)2]; and either C6H5COOH, 4-OH–C6H5COOH,
Received 31 July 2013 3,5-NO2–C6H5COOH or 2-Cl–C6H5COOH to afford the corresponding metal complexes: [Cu(C6H5COO)2
Accepted 8 November 2013 (L)2] (1), [Cu(2-Cl–C6H4COO)2(L)2] (2), [Cu(3,5-NO2–C6H3COO)2(L)2] (3), [Cu(4-OH–C6H4COO)2(L)2] (4),
Available online 19 November 2013
[Zn(C6H5COO)2(L)2] (5), [Zn(2-Cl–C6H4COO)2(L)2] (6), [Zn(3,5-NO2–C6H3COO)2(L)2] (7), [Zn(4-OH–C6H4
COO)2(L)2] (8). The diamagnetic zinc complexes were characterized by IR, NMR spectroscopy and elemen-
Keywords: tal analysis; while the paramagnetic copper complexes were only characterized by IR spectroscopy,
Pyrazole
elemental analysis and 1 and 2 were further characterized by single crystal X-ray diffraction studies.
Copper
Zinc
All eight complexes are very good initiators for the ring opening polymerization (ROP) of e-caprolactone
Initiators and D,L-lactide at elevated temperatures, under solvent-free conditions and in toluene respectively; pro-
Ring opening polymerization ducing polycaprolactone (PCL) and poly(D,L-lactide) (PLA) of moderate molecular weights (ca 4757 Da for
e-Caprolactone PCL and 2484 Da for PLA) and narrow polydispersity indices (1.36 for PCL and 1.42 for PLA). The 13C{1H}
D,L-Lactide NMR spectra indicate the stereochemistry of PLA is heterotactic.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction recently, lanthanides [12] and transition metals such as Zn [13]

Polycaprolactone (PCL) and poly(D,L-lactide) (PLA) are two very
important polymers used in agricultural, biomedical and environ-
mental fields due to their tuneable properties and biodegradability
[1]. These polyesters are mainly synthesized by ring opening poly-
merization (ROP) of the cyclic esters with coordination compounds
as catalysts. Developing catalysts that are effective and inexpen-
sive for producing these biodegradable polymers would aid in
reducing costs of producing these polymers, especially for agricul-
tural usage. Many metal complexes such as Al [2], Sn [3], Ca [4], Li
[5], Mg [6], Fe [7], Zn [8] and Zr [9] have been used as initiators/cat-
alysts for the ROP of cyclic esters. However, in many cases unde-
sired trans-esterification reactions take place, which hamper
control over the polymerization process. As a result, there is con-
tinued search for new initiators/catalysts that can yield well-
defined PCL and PLA. Tin(II) octanoate [10] and aluminium(III)
isopropoxide [11] continue to be the two standard industrial initi-
ators and also used for the study of the ROP mechanisms. More
⇑ Corresponding author.
E-mail address: jdarkwa@uj.ac.za (J. Darkwa).
and Cu [14] have been investigated as initiators. This report pro-
vides a comparison of Zn initiators to their Cu analogues.
Ligand systems also have the ability to affect the ability of a me-
tal complex to initiate the ROP of these cyclic esters. In many cases
ancillary ligands are used to tune metal complexes to aid the poly-
merization process [15]. Schiff base and b-diiminate compounds
are the most popular nitrogen-donor ancillary ligands in initiators
for lactide and lactone polymerization, primarily because they pro-
vide electrophilic metal centers for initiators to efficiently coordi-
nate monomers [16]. Pyrazole and pyrazolyl donor compounds
are being actively developed as nitrogen-donor catalysts [17],
because such compounds offer highly electrophilic metal centers.
Recent reports by Yu et al. [17b], Kang et al. [17c] and Lian et al.
[17d] indicate that pyrazolyl zinc complexes are active initiators
for the ring opening polymerization of D,L-lactide. In the current re-
port, we have combined the ability of pyrazole as nitrogen-donor
ligands and substituted benzene carboxylate as sources of metal–
oxygen bonds to zinc and coppers initiators for the ROP of e-capro-
lactone and D,L-lactide. We have also used Energy Dispersive X-ray
(EDX) analysis as a tool to determine whether the final polymers
are free of metals, especially for polymers produced with copper
initiators.

0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.11.011
56 D. Appavoo et al. / Polyhedron 69 (2014) 55–60
2. Experimental
2.1. Materials and instrumentation
Syntheses were performed under a dry nitrogen atmosphere
using standard Schlenk techniques. All solvents were of analytical
grade and were dried and distilled prior to use. Toluene and dichlo-
romethane were dried and distilled from sodium benzophenone
and P2O5 respectively. 3,5-Dimethylpyrazole, [Cu(OAc)2], [Zn(OAc)2],
C6H5COOH (benzoic acid), 4-OH–C6H5COOH (4-hydroxybenzoic
acid), 3,5-NO2–C6H5COOH (3,5-dinitrobenzoic acid), 2-Cl–C6H5
COOH (2-chlorobenzoic acid) and e-caprolactone (98%) were
obtained from Sigma–Aldrich and used as received. D,L-lactide
was obtained from Purac biochem and used as received. NMR
spectra were recorded in chloroform-d (CDCl3) and dimethylsulph-
oxide-d6 (DMSO) on a Gemini 2000 instrument (300 MHz for 1H
NMR and 75 MHz for 13C{1H} NMR) and a Bruker Ultrashield 400
instrument (400 MHz for 1H NMR and 100 MHz for 13C{1H} NMR)
at room temperature. 1H and 13C{1H} NMR chemical shifts were
referenced to the residual signals of the protons or carbons of the
NMR solvents and are quoted in d (ppm): CDCl3 at 7.24 and
77.0 ppm for 1H and 13C{1H} NMR spectra respectively; DMSO at
2.45 and 39.5 ppm for 1H and 13C{1H} NMR spectra respectively.
Coupling constants are reported in Hertz (Hz). Infrared spectra
were recorded on a Bruker FR-IR Tensor27 spectrometer fitted with
an ATP-IR probe. Elemental analyzes were performed on a Vario
Elementar microcube CHNS analyzer at Rhodes University, South
Africa. ESI-MS spectra were recorded on a Waters API Quattro Mi-
cro spectrometer at the University of Stellenbosch, South Africa.
Magnetic moments of the copper complexes were measured using
a Magway MSB MK1 magnetic susceptibility balance. The effective
magnetic moment, leff, is reported in Bohr magnetons (BM).
Molecular weight and molecular weight polydispersity of polymers
were determined by size exclusion chromatography (SEC), using a
WGE Dr. Bures Q1000 Gel Permeation Chromatograph equipped
with polystyrene gel columns using THF as an eluent, calibrated
by polystyrene standards at 40 °C.
2.2. Synthesis of zinc and copper complexes
The method used to synthesize the complexes is an adaptation
of the procedure described by Baruah for the synthesis of pyrazole
metal carboxylates [18]. It is a one pot, room temperature reaction
between a metal(II) acetate, benzoic acid and the pyrazole com-
pound. In a typical reaction the metal(II) acetate was stirred with
the benzoic acid, in a 1:2 mol ratio in methanol (15 mL) for
30 min at room temperature, after which a solution of 3,5-dimeth-
ylpyrazole (L) in toluene (5 mL) was added to the mixture and
stirred for a further 30 min. The ratio of the metal(II) acetate to
pyrazole was 1:2.
2.2.1. Synthesis of [Cu(C6H5COO)2(L)2] (1)
Complex 1 was obtained as blue crystals from the reaction of
[Cu(OAc)2] (0.20 g, 1.00 mmol), C6H5COOH (0.24 g, 2.00 mmol)
and 3,5-dimethylpyrazole (0.19 g, 2.00 mmol). Yield = 0.41 g
(82%). IR: 1627 cm 1 (mC@O). leff: 1.67 BM. ESI-MS m/z (%): 376
[M C6H5COO]+, 25. Anal. Calc. for C24H26CuN4O4.H2O: C, 55.86;
H, 5.47; N, 10.86. Found: C, 55.95; H, 5.20; N, 10.71%.
2.2.2. Synthesis of [Cu(2-Cl–C6H4COO)2(L)2] (2)
Complex 2 was prepared by reacting [Cu(OAc)2] (0.20 g,
1.00 mmol) and 2-Cl–C6H4COOH (0.31 g, 2.00 mmol) with 3,5-
dimethylpyrazole (0.19 g, 2.00 mmol). Complex 2 was obtained
as a green solid. Yield = 0.31 g (55%). IR: 1574 cm 1 (mC@O). leff:
1.87 BM. Anal. Calc. for C24H24CuCl2N4O4: C, 50.85; H, 4.27; N,
9.88. Found: C, 50.79; H, 4.12; N, 9.78%.
2.2.3. Synthesis of [Cu(3,5-NO2–C6H3COO)2(L)2] (3)
Complex 3 was synthesized using [Cu(OAc)2] (0.20 g,
1.00 mmol), 3,5-NO2–C6H3COOH (0.43 g, 2.00 mmol) and 3,5-
dimethylpyrazole (0.19 g, 2.00 mmol) and isolated as a green solid.
Yield = 0.45 g (66%). IR: 1620 cm 1 (mC@O). Anal. Calc. for C24H22N8-
O12Cu
(1/3 mol)C7H8: C, 44.63; H, 3.51; N, 15.81. Found: C, 44.85;
H, 3.63; N, 15.74%.
2.2.4. Synthesis of [Cu(4-OH–C6H4COO)2(L)2] (4)
The reaction of [Cu(OAc)2] (0.20 g, 1.00 mmol), 4-OH–C6H4-
COOH (0.28 g, 2.00 mmol) and 3,5-dimethylpyrazole (0.19 g,
2.00 mmol) gave 4 as a green solid. Yield = 0.33 g (62%). IR:
1674 cm 1 (mC@O). Anal. Calc. for C24H26CuN4O6
4CH3OH: C,
51.09; H, 6.43; N, 8.51. Found: C, 50.74; H, 5.49; N, 8.50%.
2.2.5. Synthesis of [Zn(C6H5COO)2(L)2] (5)
Reaction of [Zn(OAc)2] (0.18 g, 1.00 mmol), C6H5COOH (0.24 g,
2.00 mmol) and 3,5-dimethylpyrazole (0.19 g, 2.00 mmol) gave 5
as white crystals. Yield = 0.40 g (80%). 1H NMR (CDCl3): d 2.24 (s,
12H, CH3-pz); 5.91 (s, 2H, CH-pz); 7.36 (t, 3JHH = 14.8 Hz, 4H, 3,5-
Bz); 7.43 (t, 3JHH = 14.8 Hz, 2H, 4-Bz); 8.14 (d, 3JHH = 7.2 Hz, 2,6-
Bz). 13C{1H} NMR (CDCl3): d 11.9; 105.8; 127.8; 130.1; 131.2;
135.0; 173.6. ESI-MS m/z (%): 379 [M C6H5COO]+, 50. IR:
1609 cm 1 (mC@O). Anal. Calc. for C24H26N4O4Zn: C, 57.66; H, 5.24;
N, 11.21. Found: C, 57.60; H, 5.39; N, 11.24%.
2.2.6. Synthesis of [Zn(2-Cl–C6H4COO)2(L)2] (6)
Complex 6 was synthesized using [Zn(OAc)2] (0.18 g,
1.00 mmol), 2-Cl–C6H4COOH (0.31 g, 2.00 mmol) and 3,5-dimeth-
ylpyrazole (0.19 g, 2.00 mmol) and isolated as a white solid.
Yield = 0.36 g (64%). 1H NMR (CDCl3): d 2.15 (s, 12H, CH3-pz);
5.85 (s, 2H, CH-pz); 7.34 (d, 3JHH = 6.1 Hz, 2H, 3-CH-Bz); 7.43 (t,
3
JHH = 14.0 Hz, 4H, 4,5-CH-Bz); 7.70 (d, 3JHH = 5.8 Hz 2H, 6-CH-Bz).
13
C{1H} NMR (CDCl3): d 11.8; 104.0; 126.9; 130.1; 131.0; 143.8;
149.2. IR: 1635 cm 1 (mC@O). Anal. Calc. for C24H24Cl2N4O4Zn: C,
50.68; H, 4.25; N, 9.85. Found: C, 50.99; H, 4.31; N, 9.45%.
2.2.7. Synthesis of [Zn(3,5-NO2–C6H3COO)2(L)2] (7)
Complex 7 was prepared using [Zn(OAc)2] (0.18 g, 1.00 mmol),
3,5-NO2–C6H3COOH (0.43 g, 2.00 mmol) and 3,5-dimethylpyrazole
(0.19 g, 2.00 mmol). Compound 7 was isolated as a white solid
after filtration and evaporation of the solvent from the filtrate.
Yield = 0.40 g (59%). 1H NMR (DMSO): d 2.12 (s, 6H, CH3-pz); 5.76
(s, 2H, CH-pz); 8.91 (s, 6H, 2,4,6-Bz). 13C{1H} NMR (DMSO): d
11.8; 103.8; 120.6; 129.0; 138.5; 148.1; 166.5. IR: 1625 cm 1
(mC@O). Anal. Calc. for C24H22N4O12Zn: C, 42.40; H, 3.26; N, 16.48.
Found: C, 42.18; H, 3.24; N, 16.44%.
2.2.8. Synthesis of [Zn(4-OH–C6H4COO)2(L)2] (8)
Reaction of [Zn(OAc)2] (0.18 g, 1.00 mmol), 4-OH–C6H4COOH
(0.28 g, 2.00 mmol) and 3,5-dimethylpyrazole (0.19 g, 2.00 mmol)
gave 3 as a white solid. Yield = 0.32 g (60%). 1H NMR (CDCl3): d
2.12 (s, 6H, 5-CH3-pz); 2.43 (s, 6H, 3-CH3-pz); 6.01 (s, 2H, CH-
pz); 8.12 (s,br, 4H, 3,5-Bz); 8.25 (s,br, 4H, 2,6-Bz). 13C{1H} NMR
(CDCl3): d 11.7; 12.4; 105.2; 115.0; 123.8; 131.8; 145.0; 149.3;
161.1; 170.0; 174.2. IR: 1624 cm 1 (mC@O). Anal. Calc. for C24H26N4-
O6Zn.CH3OH: C, 53.24; H, 5.36; N, 9.93. Found: C, 53.43; H, 5.44; N,
9.49%.
2.3. Molecular structure determination by single crystal X-ray analysis
Single-crystal X-ray diffraction data for 1 and 2 were collected
on a Bruker APEXII diffractometer with Mo Ka (k = 0.71073 Å)
 D. Appavoo et al. / Polyhedron 69 (2014) 55–60 57

radiation and diffractometer to crystal distance of 4.00 cm. The ini-
tial cell matrix was obtained from three series of scans at different
starting angles. Each series consisted of 12 frames collected at
intervals of 0.5° in a 6° range about with an exposure time of
10 s per frame. The reflections were successfully indexed by an
automated indexing routine built in the APEXII program suite. The
data were collected using the full sphere data collection routine
to survey the reciprocal space to the extent of a full sphere to a res-
olution of 0.75 Å. Data were harvested by collecting 2982 frames at
intervals of 0.5° scans in x and u with exposure times of 10 s per
frame [19]. A successful solution by the direct methods of SHELXS97
provided all non-hydrogen atoms from the E-map. All non-hydro-
gen atoms were refined with anisotropic displacement coefficients.
All hydrogen atoms were included in the structure factor calcula-
tion at idealized positions and were allowed to ride on the neigh-
bouring atoms with relative isotropic displacement coefficients
[20].
2.4. Polymerization of e-caprolactone and D,L-lactide
Polymerization of e-caprolactone and D,L-lactide were per-
formed on a 12-tube Radley’s parallel reactor, using a [mono-
mer]:[initiator] ([M]/[I]) ratios of 100:1 and 50:1 respectively.
While the D,L-lactide polymerizations were typically performed
with D,L-lactide (1.44 g, 0.01 mol) and in toluene (2.5 mL), the cap-
rolactone reactions were performed with (1.14 g, 0.01 mol) of e-
caprolactone in a solvent-free medium. Both reactions were run
at 110 °C. After the required reaction time, the reaction mixture
was quenched by rapid cooling to room temperature with liquid
nitrogen. The solvent was removed in vacuo and percentage con-
versions determined from the 1H NMR spectra of the polymers.
The PLA was purified by first dissolving the crude product in
dichloromethane (15 mL) and adding a hydrochloric acid solution
in methanol (0.5 M, 15 mL) to the mixture. The solution was sha-
ken vigorously and allowed to separate and the aqueous layer
washed with dichloromethane (3  10 mL). The combined organic
layer was then washed with distilled water (15 mL), followed by
sodium hydroxide solution (1.0 M, 15 mL) and lastly with CH2Cl2
(3  10 mL). After drying the organic layer over anhydrous magne-
sium sulfate, the solvent was removed in vacuo to give a fluffy
white solid. Purification of PCL was a lot simpler. The polymers
were purified by first dissolving the crude product in CH2Cl2, fol-
lowed by the addition of cold methanol to give a white precipitate.
In all cases Energy Dispersive X-ray (EDX) analysis was run after
the purification to determine whether there were remnants of the
catalysts in the polymers. Scanning Electron Micrographs (SEM)
provided data on the morphology of the polymers.
3. Results and discussions
3.1. Synthesis of pyrazole metal carboxylates
Reactions of copper(II) and zinc(II) acetates with substituted
benzene carboxylic acids and subsequently with 3,5-dimethylpyr-
azole produced bis(pyrazole)metal carboxylates of the respective
metal as depicted in Scheme 1. These reactions are driven by the
elimination of acetic acid from the metal acetate, and most likely
go through an initial formation of metal benzoates followed by a
reaction with the pyrazole that produces the final product. The
one pot reaction provides a very facile route to making these pyr-
azole metal carboxylates in very good yields.
The copper complexes (1–4) were characterized by IR, magnetic
moment measurements, elemental analysis whereas single crystal
X-ray diffraction studies were used to establish the structures of 1
and 2. In all complexes the benzoate carbonyl peaks generally
shifted by 20 cm 1 compared to the corresponding benzoic acid.
For example, complex 2 has a carbonyl peak at 1574 cm 1, com-
pared to a similar peak at 1591 cm 1 in the corresponding carbox-
ylic acid. All four copper complexes are paramagnetic as they
showed very broad peaks in their 1H NMR spectra because of their
paramagnetic properties. For example, the effective magnetic mo-
ment of 1.87 BM for complex 2 at room temperature is as expected
for one unpaired electron located on the Cu(II) ion in this complex.
Single crystal X-ray crystallography confirmed structures
proposed from elemental analysis data. Crystallographic data and
selected bond lengths and angles are in Tables 1 and 2 respectively.
The molecular geometries of 1 and 2 show four-coordinate copper
complexes with cis-coordination of the two benzoates and the two

O2N

Cl
HN N O NO2
M HN N O
O O M
HN N O
HN N O
O NO2
O
(M = Cu (3), Zn (7))
3,5-NO2-C6H3COOH L Cl
O2N
(M = Cu (2), Zn (6))
L 2-Cl-C6H4COOH
[M(OAc)2]
4-OH-C6H4COOH
L
L
OH C6H5COOH

HN N O HN N O
M M
O O O
HN N HN N O

O NH O
L= N
(M = Cu (4), Zn (8)) OH
(M = Cu (1), Zn (5))

Scheme 1. Synthesis of pyrazole copper and zinc carboxylate complexes.

58 D. Appavoo et al. / Polyhedron 69 (2014) 55–60

Table 1
Crystal data and structure refinement parameters for 1 and 2.

Complex 1 2
Empirical formula C24H24N4O4Cu C24H24Cl2N4O4Cu
Formula weight 498.03 566.91
T (K) 100(2) 100(2)
k (Å) 0.71073 0.71073
Crystal system monoclinic monoclinic
Space group P21/n C2/c
a (Å) 15.968(12) 23.468(4)
b (Å) 10.809(9) 10.1880(16)
c (Å) 16.095(13) 11.6142(18)
a (°) 90 90
b (°) 108.44(5) 119.046(3)
c (°) 90 90
V (Å3) 3635.7(5) 2427.6(7)
Z 4 4
Dcalc (Mg/m3) 1.255 1.551
Absorption coefficient (mm 1) 0.862 1.159
F(0 0 0) 1036 1164
Crystal size (mm3) 0.51  0.19  0.13 0.10  0.08  0.07
h Range for data collection (°) 2.45–27.09 1.99–28.39
Index ranges 20 6 h 6 20, 13 6 k 6 13, 20 6 l 6 20 31 6 h 6 30, 11 6 k 6 13, 15 6 l 6 15
Reflections collected 34 499 12 439
Independent reflections 5755 [R(int) = 0.0334] 3050 [R(int) = 0.0504]
Completeness to h (°, %) 27.09 (99.0) 28.39 (99.0)
Absorption correction numerical with SADABS semi-empirical from equivalents
Maximum and minimum transmission 0.8954 and 0.6670 0.9233 and 0.8929
Refinement method full-matrix least-squares on F2 full-matrix least-squares on F2
Data/restraints/parameters 5755/0/302 3050/0/161
Goodness-of-fit (GOF) on F2 0.981 1.034
Final R indices [I P 2r(I)] R1 = 0.0303, wR2 = 0.0827 R1 = 0.0367, wR2 = 0.0867
R indices (all data) R1 = 0.0349, wR2 = 0.0855 R1 = 0.0532, wR2 = 0.0951
Largest difference peak and hole (e Å 3) 0.386 and 0.383 0.783 and 0.570

Table 2
Selected bond lengths (Å) and bond angles (°) for complexes 1 and 2.

1 2
Cu(1)–O(1) 1.9966(18) N(1)–Cu(1) 1.9815(18)
Cu(1)–N(3) 1.979(2) O(1)–Cu(1) 1.9855(15)
Cu(1)–N(1) 1.986(2) C(6)–O(2) 1.248(3)
Cu(1)–O(3) 1.9944(19) C(6)–O(1) 1.273(3)
O(1)–C(1) 1.267(2) C(6)–O(1)–Cu(1) 102.96(14)
O(2)–C(1) 1.2517(19) N(1)–Cu(1)–N(1)#1 92.39(11)
O(4)–C(8)–O(3) 121.89(14) N(1)–Cu(1)–O(1) 91.22(7)
O(2)–C(1)–O(1) 122.04(15) N(1)#1–Cu(1)–O(1) 161.93(7)
N(3)–Cu(1)–N(1) 90.93(8) N(1)#1–Cu(1)–O(1)# 91.22(7)
N(3)–Cu(1)–O(3) 90.47(8) O(1)–Cu(1)–O(1)#1 90.81(9)
N(1)–Cu(1)–O(3) 177.72(5)
N(3)–Cu(1)–O(1) 176.61(5)
N(1)–Cu(1)–O(1) 92.36(8)
O(3)–Cu(1)–O(1) 86.27(7)

pyrazoles (Figs. 1 and 2). Baruah and co-workers [21] have

reported the accidental co-crystallization of a four-coordinate
complex cis-[(3,5-Me 2 pz) 2 Cu(Bz) 2 ] (A) and a five-coordinate
trans-[(3,5-Me2pz)2Cu(Bz)2(OH2)] (where 3,5-Me2pz = 3,5-dimeth-
ylpyrazole and Bz = benzoate) in a Cu(II) catalysed cleavage of a
carbon–nitrogen bond in N-benzoyl-3,5-dimethylpyrazole. The
geometry of complex 1, very similar to structure A reported by
Baruah, crystallizes as a solvate with an unidentified solvent (see
Supporting information). Complexes 1 and A can be superimposed
with a rmsd of 0.495 Å. Complexes 1, 2, and A are square planar,
however the planarity is disrupted in 2 and A. Namely, the dihedral
angle between the triangular Cu, O, O plane and the triangular
plane Cu, N, N is 2.04° in 1, 11.78° in A, and 25.28° in 2. In all three
complexes there are distal Cu


O interactions from the metal cen-
ter to the would-be apical sites occupied by the uncoordinated
oxygen atoms of the carboxylate ligands. These Cu


O distances
are 2.480(6) Å in 1, 2.542 Å in A and 2.562 Å in 2. The Cu–O
Fig. 1. Molecular structure of 1 shown with 50% thermal probability ellipsoids. All
H atoms are omitted for clarity.
distances to the coordinated oxygen atoms are much shorter at un-
der 2.0 Å in the three complexes. The Cu–N distances are also typ-
ical and closely group around 1.98 Å. In the crystals of the three
compounds the Cu complexes form similar one-dimensional
hydrogen-bonded chains.
The zinc complexes are diamagnetic and could be characterized
by NMR spectroscopy; showing typical peaks associated with both
ligands on complexation to a metal. The characterization of these
complexes was further supported by IR and elemental analysis.
 D. Appavoo et al. / Polyhedron 69 (2014) 55–60 59

Fig. 3. ROP of e-CL using 1 and 3 as initiators at [M]/[I] = 50:1.

Table 4
ROP of D,L-lactide in toluene using complexes 1–8.
1
Entry Complex % Conversion kapp (h ) Mn (1H NMR) Mn (SEC)a PDI
1 1 94 0.039 1780 1232 1.84
2 2 93 0.020 1650 – –
3 3 92 0.018 1810 1167 1.87
4 4 92 0.020 1242 – –
5 5 96 0.024 1900 1971 2.05
6 6 95 0.023 1342 – –
Fig. 2. Molecular structure of 2 shown with 50% thermal probability ellipsoids. 7 7 96 0.025 1645 833 2.35
8 8 96 0.023 1342 – –

Conditions: [M]/[I] = 100:1 at 110 °C after 144 h.

3.2. Ring opening polymerization activity a
Using a correction factor 0.58 for Mn.

3.2.1. e-Caprolactone
Complexes 1–8 were all investigated for their activities in the
bulk polymerization of e-CL at 110 °C using [M]/[I] = 50:1; leading
to high conversions of the monomer to polycaprolactone (PCL)
(Table 3 and Fig. 3). Metal-carboxylates as initiators are normally
used in conjunction with an alcohol to produce a metal–alkoxide
bond required to initiate the ring opening polymerization of the
cyclic ester monomers, according to the mechanistic studies
carried out by several research groups [16c]. We did not add
alcohol in order to investigate the effect of substituents on the
aromatic ring of the benzoic acid since the metal-carboxylates also
have the requisite metal–oxygen bond for initiation of the polymer-
ization process. The substituents on the benzoic acid further pro-
vided us with a way to vary the electrophilicity of the metal center
in the initiators. Benzoic acids with electron-withdrawing groups
were expected to lead to initiators that were more electrophilic.
Generally the zinc complexes were better initiators for the poly-
merization of caprolactone than their copper analogues. The sub-
stituent on the carboxylate ligand also had a big effect on the
rate of polymerization. For example the copper initiator 1, without
an electron-withdrawing substituent, was at least four orders of
magnitude slower in initiating the polymerization of the caprolac-
tone when compared to the initiator 3 that has two electron-with-
drawing nitro groups (Fig. 3).
1
H NMR spectroscopy and size exclusion chromatography (SEC)
were used to determine the Mn values of the PCL produced
(Table 3). All the Mn from NMR data were lower than Mn from
SEC measurement and nearly all the Mn values from NMR are lower
than Mn determined from SEC and similar to observations were
made by others using 1H NMR data to estimate molecular weights
of PCL and PLA [22]. The highest Mn, determined by SEC is from 1
as initiator (4757 Da, PDI = 1.36) and the lowest Mn was shown
by initiator 2 (3125 Da, PDI = 1.84). These molecular weights
are much lower than compared to molecular weight obtained
with (pyrazolylphenylimino)phenoxy Al (Mn = 211 000 Da) and Zn
(Mn = 181 000 Da) initiators [23]; suggest chain termination in
our initiators is very facile. Nonetheless such low molecular weight
polymers can find useful applications where toughness is not a
requirement. The formation of low molecular weight polymers is
also indicative of a non-living polymerization process.

Table 3
Bulk ROP of e-CL using Cu and Zn complexes. 3.2.2. D,L-Lactide
a 1 1 b
The ROP of D,L-lactide using the Cu and Zn complexes (1–8)
Entry Complex Time (h) kapp (h ) Mn ( H NMR) Mn (SEC) PDI
were much slower than the ROP of e-caprolactone (Table 4 and
1 1 30 0.090 4242 4734 1.36 Fig. 4), which is not surprising because of the larger ring size of
2 2 29 0.151 2866 – –
the caprolactone. Whereas it took the slowest initiator, 1, to com-
3 3 14 0.286 2514 3450 1.61
4 4 27 0.143 4742 – –
pletely convert CL to PCL in 30 h, it took the same initiator 144 h to
5 5 27 0.185 4405 4757 1.69 have 94% conversion of LA to PLA. However, unlike the CL polymer-
6 6 26 0.182 1817 – – ization the activities of all the initiators for LA polymerization were
7 7 26 0.120 1676 3125 1.84 similar (Fig. 4). The molecular weights of these polymers are much
8 8 25 0.169 2026 – –
lower than PLA from common initiators such as [Al(OiPr)3],
Conditions: [M]/[I] = 50:1, Temp. = 110 °C. (Mn = 90 000 Da) [24] and [Sn(Oct)2] [25] (Mn = 130 000 Da). Poly-
a
Time required for complete polymerization. lactide from 5 had the highest Mn (2484 Da, PDI = 2.05). The stereo-
b
Using a correction factor 0.56 for Mn.
chemistry of the PLA formed was determined from the 13C{1H}
60 D. Appavoo et al. / Polyhedron 69 (2014) 55–60
% Conversion
100
80 Iniator 1
60 Iniator 8
40
20
0 Time (h)
0 10 20 30 40 50
Fig. 4. OP of D,L-lactide in toluene using complexes 1 and 8.
NMR spectra of the polymers. Based on the comparisons with the
literature values it was concluded that the PLA produced by com-
plexes 1–8 are predominantly heterotactic [26].
One of the problems associated with using metal initiators is
the possibility of having trace metals in the polymers isolated.
Although zinc is bio-friendly and thus having traces of zinc in
a polymer for biological use should not be a problem, copper
is not bio-friendly. As such we purified all the polymers pro-
duced and performed energy dispersive X-ray (EDX) analysis
on these samples to determine if the polymers isolated were
free of metals from the initiators. A typical EDX analysis data
is given in Fig. S2 in the supplementary materials. In all such
measurements we found no metals or only trace amount in
the polymers; confirming that purification processes used pro-
duced metal-free polymers.
4. Conclusion
All the copper and zinc complexes synthesized are good initia-
tors and initiate the ring opening polymerization of both e-capro-
lactone and D,L-lactide to polycaprolactone and polylactide
respectively. The activities of the complexes varied with respect
to the metal but there is no clear cut variation in the activities of
initiators based on substituents on the benzoic acids that were
used as ancillary ligands to introduce a metal–oxygen bond re-
quired for the polymerization. Generally the zinc complexes
showed better activities than their copper analogues. The polymers
obtained have low molecular weights, with narrow molecular
weight distributions suggesting some control in the polymeriza-
tion process; but, the stereochemistry of the polylactide is predom-
inantly heterotactic.
Acknowledgements
We acknowledge financial support for this work from Univer-
sity of Johannesburg. We thank Dr. Ravin Narain at the University
of Alberta, Canada for the polymer molecular weight
measurements.
Appendix A. Supplementary data
CCDC 953410 and 953411 contain the supplementary crystallo-
graphic data for 1 and 2. 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, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336 033; or e-mail: depos-
it@ccdc.cam.ac.uk. A typical 13C{1H}NMR spectrum for the
determination of stereochemistry of PLA is provided as supple-
mentary material Supplementary data associated with this article
can be found, in the online version, at http://dx.doi.org/10.1016/
j.poly.2013.11.011.
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