Binuclear Schiff-base zinc(II) complexes: Synthesis, crystal structures and reactivity toward ring opening polymerization of rac-lactide

Article abstract of DOI:10.1016/j.poly.2019.01.043

Upon crystallization from DMF/diethyl ether or CH₂Cl₂/pyridine of tetracoordinated Zn(II) complexes containing either 4-fluorophenyl or 4-anisyl substituted O,N,O-tridentate Schiff base ligands and pyridine as auxiliary ligand, three new doubly phenoxide-bridged dimeric Zn(II) complexes were isolated and their catalytic properties for the ring opening polymerization (ROP) of rac-lactide were explored. The single-crystal XRD analysis allowed to corroborate the molecular structures of the binuclear complexes, showing that the pentacoordinated Zn(II) metal ion adopts a slightly distorted square pyramidal geometry. The basal plane Is formed by the O,N,O-donor set of the tridentate Schiff base ligand and a phenoxo bridging oxygen, while a pyridine or a DMF molecule is located at the apex of the pyramid. The binuclear complexes were employed as catalysts in the ROP of rac-lactide for polylactide (PLA) synthesis. Polymerization conditions such as reaction time, catalyst concentration and use of benzyl alcohol as cocatalyst were studied, as well as their influence on the conversion rate, average molecular weight and polydispersity of the obtained PLA. The catalyst substituted with fluorine was more reactive, but with a lower control on the molecular weight compared to the methoxy-substituted catalyst. On the other hand, the presence of pyridine as an auxiliary ligand generates an improvement in the polydispersity of PLA.

Full text of DOI:10.1016/j.poly.2019.01.043

Accepted Manuscript
Binuclear Schiff-Base Zinc(II) complexes: Synthesis, crystal structures and re-
activity toward ring opening polymerization of rac-Lactide
Darío M. González, Jonathan Cisterna, Iván Brito, Thierry Roisnel, Jean-René
Hamon, Carolina Manzur
PII:
S0277-5387(19)30058-0
https://doi.org/10.1016/j.poly.2019.01.043
POLY 13716
DOI:
Reference:
Polyhedron
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Received Date:
Revised Date:
Accepted Date:
25 August 2018
15 January 2019
17 January 2019
Please cite this article as: D.M. González, J. Cisterna, I. Brito, T. Roisnel, J-R. Hamon, C. Manzur, Binuclear Schiff-
Base Zinc(II) complexes: Synthesis, crystal structures and reactivity toward ring opening polymerization of rac-
Lactide, Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.2019.01.043
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Binuclear Schiff-Base Zinc(II) complexes: Synthesis, crystal structures and reactivity toward
ring opening polymerization of rac-Lactide
Darío M. González *,a, Jonathan Cisterna b, Iván Brito b, Thierry Roisnel c, Jean-René Hamon c,
Carolina Manzur a
a
Instituto de Química, Pontificia Universidad Católica de Valparaíso, Campus Curauma, Avenida Universidad 330,
Valparaíso, Chile
b
Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Avda. Universidad de
Antofagasta 02800, Campus Coloso, Antofagasta, Chile
c Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) – UMR 6226, F-35000 Rennes, France
This paper is dedicated to Prof. David Carrillo (PUCV), a highly esteemed mentor, colleague, and
friend at the occasion of his 80th birthday.
* Corresponding author.
e-mail address: dario.gonzalez@pucv.cl (D.M. González)
Abstract
Upon crystallization from DMF/diethyl ether or CH2Cl2/pyridine of tetracoordinated Zn(II)
complexes containing either 4-fluorophenyl or 4-anisyl substituted O,N,O-tridentate Schiff base
ligands and pyridine as auxiliary ligand, three new doubly phenoxide-bridged dimeric Zn(II)
complexes were isolated and their catalytic properties for the ring opening polymerization (ROP) of
rac-lactide were explored. The single-crystal XRD analysis allowed to corroborate the molecular
structures of the binuclear complexes, showing that the pentacoordinated Zn(II) metal ion adopts a
slightly distorted square pyramidal geometry. The basal plane Is formed by the O,N,O-donor set of
the tridentate Schiff base ligand and a phenoxo bridging oxygen, while a pyridine or a DMF
molecule is located at the apex of the pyramid. The binuclear complexes were employed as catalysts
in the ROP of rac-lactide for polylactide (PLA) synthesis. Polymerization conditions such as
reaction time, catalyst concentration and use of benzyl alcohol as cocatalyst were studied, as well as
their influence on the conversion rate, average molecular weight and polydispersity of the obtained
PLA. The catalyst substituted with fluorine was more reactive, but with a lower control on the
molecular weight compared to the methoxy-substituted catalyst. On the other hand, the presence of
pyridine as an auxiliary ligand generates an improvement in the polydispersity of PLA.
Keywords: Binuclear Zinc complexes; Schiff-Base ligands: X-ray diffraction; Ring opening
polymerization; Polylactide

1. Introduction
The development of biodegradable polymers is currently a subject of great scientific interest, as it
points to the possibility of replacing some applications of traditional petrochemical plastic
materials. In this context, in the last decade, polylactide (PLA) is one of the most promising and its
research has grown significantly since in addition to its biodegradable characteristics, it is also
biocompatible and of bio-sourced origin [1–5]. Another important characteristic of PLA is that it
can achieve physical properties and mechanical behaviors similar to that of polyolefins when
synthesized by ring-opening polymerization (ROP) from a lactide (LA) monomer unit using a
suitable catalytic system [6–9]. The catalysts used for PLA synthesis have evolved over time: the
first catalysts were metals like tin alkoxides [9–11], and have since reached increasingly complex
species like some organometallic compounds, and, more recently, coordination complexes [12].
There are currently a wide variety of metal complexes that have been studied as ROP catalysts, with
general success in the use of Al as a metal center [13–19], some alkaline [20–22]and alkaline earth
metals [23–25],and also some transition metals like Ti or Zr [26]. However, Zinc-based complexes
are among the most outstanding, mainly because of good polymerization control via ROP, which
translates into good catalytic activity, high molecular weight, low polydispersity, and even
stereochemical control of synthesized PLA [27–33].In addition, Zn has low toxicity compared to
other metals.
With respect to the design of a coordination complex for ROP catalysis, the choice of central metal
atom is undoubtedly a highly determining factor; that said, ligands also have an important role in
the catalytic behavior of the complex, influencing reactivity and even some structural characteristics
of the synthesized polymers [23,34]. Furthermore, the development of numerous synthesis routes
has allowed a wide variety of coordination compounds to exist today, e.g., ligands with different
structures, symmetries, chelating heteroatoms, and substituent groups. Because of this, the range of
complexes used in ROP catalysis has grown enormously, though without consensus on the real
influence of metal complex structure in ROP. Rather, it is generally only possible to approximate
catalyst functions as a set of structural variables, taken from different polymerization experimental
conditions, optimized for the use of each catalyst.
To this end, this paper proposes the use of Schiff-base ligands derived from β-diketones. The latter
are characterized as versatile molecules and very good coordinators, with the ability to stabilize a
wide variety of metals in different oxidation states. In addition, their simple synthesis routes are of
good performance and so are easily functionalized [35–39]. Considering the good results found with
Zinc in ROP reactions, the objective is to study Schiff-base ligands and their respective complexes

with different substituent groups, such as fluorine and methoxyl, and to subsequently evaluate their
catalytic activity in rac-LA polymerization in terms of catalytic performance, molecular weights
and polydispersities in obtained PLA.
2. Experimental
2.1.General experimental methods
Reactions were performed under dry dinitrogen atmosphere using standard Schlenk lines. Solvents
were dried and distilled according to standard procedures [40]. 1-(4-methoxyphenyl)-1,3-
butanedione [41], 1-(4-fluorophenyl)-1,3-butanedione [42], and the Schiff base proligand 4-MeO-
C6H4-C(O)CH=C(CH3)N(H)-C6H4-2-OH (1) [38], were synthesized according to literature
procedures. All other chemicals were purchased from commercial sources and used without further
1
purification. H NMR spectra were recorded at 298 K with a Bruker 300 FT-NMR spectrometer.
Chemical shifts (δ) are reported in parts per million (ppm) and referenced to the residual deuterated
solvent peaks (CDCl3: δ=7.26 ppm; (CD3)2SO: δ=2.50 ppm). Coupling constants (J) are reported in
Hertz (Hz), and integrations are reported as number of protons. High resolution electrospray
ionization mass spectra (ESI-MS) were obtained at the Centre Regional de Mesures Physiques de
l’Ouest (CRMPO, Université de Rennes 1, France) with a Thermo Fisher Scientific Q-Exactive
mass spectrometer. Elemental analyses were conducted on a Thermo-Finnigan Flash EA 1112
CHNS/O analyzer of the CRMPO Microanalytical Service. Melting points were measured in
evacuated capillaries on a Kofler Bristoline melting point apparatus and were not corrected. GPC
measurements were performed on a Shimadzu DGU-20A3R with a Shimadzu RID-10A RI detector
and a combination two-column Shimadzu Shim-pack GPC-800DP and GPC-80MD.The molecular
weight and polydispersity index were calculated according to polystyrene standards.
2.2.Synthesis of Schiff base proligand 2 and complexes
2.2.1. Synthesis of O,N,O-tridentate Schiff base proligand 2:
(4-F-C6H4)-C(O)CH=C(CH3)N(H)-C6H4-2-OH
A three necked round bottom flask equipped with a Dean-Stark apparatus was loaded with a
magnetic stir bar, 1000 mg (5,6 mmol) of 1-(4-fluorophenyl)-butane-1,3-dione, 672 mg (6.2
mmol) of 2-aminophenol, and 50 mL of toluene. The reaction mixture was refluxed for 5 h.
After cooling to room temperature, 10 mL of diethyl ether were added and the solution was
stored at −30 °C causing the precipitation of microcrystalline yellow solid. This material was

collected by filtration, washed with 3 x 2 mL portion of diethyl ether/pentane mixture (1:1), and
1
dried under vacuum, providing 1338 mg (86% yield). M.p. 118-120°C. H NMR (300 MHz,
CDCl3): 1.77 (s, 3 H, CH3), 5.70 (s, 1 H, CH=C), 6.89 (td, J=7.5 Hz, J=1.4 Hz, 1 H, C6H4-2),
7.05 (td, J=8.0 Hz, J=1.2 Hz, 2 H, F-C6H4), 7.13(m, 2 H, C6H4-2), 7.21(m, 1 H, C6H4-2), 7.90
(m, 2 H, F-C6H4) and 12.35 (s, 1 H, NH).
2.2.2. Synthesis of mononuclear complex 3 and 4:
[{4-MeO-C6H4-C(O)CH=C(CH3)N-C6H4-2-O}ZnII{NC5H5}] (3) and [{4-F-C6H4-
C(O)CH=C(CH3)N-C6H4-2-O}ZnII{NC5H5}] (4)
A Schlenk tube with a magnetic stir bar was loaded with Schiff base proligand 1 or 2 (0.71 mmol),
potassium tert-butoxide (2.1 mmol), and 3 mL of THF. The reaction mixture was stirred for 15 min,
with a dark red precipitate observed. Then, 2.1 mmol of pyridine was slowly added, and after 15
min of stirring, a solution of Zn(NO3)2x6H2O (1.1 mmol) in 1.5 mL of THF was added. The
reaction mixture was vigorously stirred for 4 h at room temperature. The solvent was then
evaporated to dryness under reduced pressure. The solid residue was dissolved in dichloromethane
and filtered to remove excess salts. The solution was evaporated to dryness, yielding a solids
sample of 3 or 4, respectively.
Compound 3: yellow solid; 200 mg (66% yield). 180°C (Dec.). Anal. Calcd for C22H20N2O3Zn
(425.79 g mol-1): C, 62.06; H, 4.73; N, 6.58. Found: C, 60.95; H, 4.68; N, 6.18. ESI-MS (m/z) calcd
64
1
for C22H20N2O3 Zn: 424.07599, found: 424.0760 (0 ppm). H NMR (300 MHz, DMSO-d6): 2.32
(s, 3 H, CH3), 3.82 (s, 3 H, OCH3), 5.70 (s, 1 H, CH=C), 6.53 (t, J=7.3 Hz 1 H, C6H4-2), 6.86 (t, J=
7.3 Hz, 1 H, C6H4-2), 7.01 (d, J=8.7 Hz, 2 H, 4-C6H4O), 7.07 (d, J=8.0 Hz, 1 H, C6H4-2), 7.18 (d,
J=7.7 Hz 1 H, C6H4-2), 7.40 (m, 2 H, C5H5N), 7.80 (m, 1 H, C5H5N), 7.93 (d, J=8.7 Hz, 2 H, C6H4-
2), and 8.58 (m, 2 H, C5H5N).
Compound 4: orange solid; 153 mg (52% yield). 200°C (Dec.). Anal. Calcd for C21H17FN2O2Zn
(413.76 g mol-1): C, 60.96; H, 4.14; N, 6.77. Found: C, 59.90; H, 4.11; N, 6.55. ESI-MS (m/z) calcd
for C21H17N2O2F64Zn: 412.056, found: 412.0559 (0 ppm). 1H NMR (300 MHz, DMSO-d6): 2.32(s, 3
H, CH3), 5.72 (s, 1 H, CH=C), 6.53 (m, 1 H, C6H4-2), 6.88 (m, 1 H, C6H4-2), 7.08 (m, 1 H, C6H4-
2),7.16 (m, 1 H, C6H4-2) 7.27 (m, 2 H,(4-C6H4F), 7.42 (m, 2 H, C5H5N), 7.82 (m, 1 H, C5H5N ),
8.00 (m, 2 H, 4-C6H4F), 8.57 (m, 2 H, C5H5N).

2.2.3. Binuclear complexes obtained by recrystallization: Compounds 5,6, and 7.
Complex 5 was obtained by slow evaporation of a saturated solution of compound 4 (100 mg) in
CH2Cl2/pyridine (10:1) as orange monocrystals. This methodology requires a filtration procedure
with celite to obtain an adequate and completely translucent solution, causing product losses and
generating overall yields of 30%. For complexes 6 and 7, 100 mg of compounds 3 and 4,
respectively, were dissolved in the minimum amount of DMF and subjected to slow vapor diffusion
of diethyl ether for up to 7 days, yielding dark orange monocrystals of complexes 6 and 7. The
overall yield reached 35%, through increasable up to 40% via recovery and concentration of the
mother liquor and repeated recrystallization processes. All compounds were characterized via
single-crystal XRD, corroborating their binuclear structures.
2.3.X-ray crystal structure determination
Some suitable crystals of compounds 5–7 were measured and their diffraction data were collected at
295(2) K on a Bruker D8 QUEST and D8 Venture diffractometer equipped with a bidimensional
CMOS Photon100 detector, using graphite monochromated Cu-K(λ = 1.54178 Å) and Mo-K(λ =
0.71073 Å) radiation, respectively. The diffraction frames were integrated using the APEX3
package [43] and were corrected for absorptions with SADABS. The structures of 5 – 7 were solved
by intrinsic phasing [44] using the OLEX 2 program [45]. All the structures were then refined with
full-matrix least-square methods based on F2 (SHELXL-2014)[44]. For the three compounds, non-
hydrogen atoms were refined with anisotropic displacement parameters. All hydrogen atoms were
included in their calculated positions, assigned fixed isotropic thermal parameters and constrained
to ride on their parent atoms. A summary of the details about crystal data, collection parameters and
refinement are documented in Table 1, and additional crystallographic details are in the CIF files.
ORTEP views were drawn using OLEX2 software [45].
Table 1. Crystal data parameters for compounds 5–7.
Compound
5
6
7
Empirical Formula
Formula mass, g mol-1
Collection T, K
crystal system
space group
a (Å)
b (Å)
c (Å)
α(°)
C42H34F2N4O4Zn2
827.47
295(2)
Orthorhombic
Pbca
16.771(3)
9.8456(17)
22.075(4)
90
90
90
C40H44N4O8Zn2
839.53
295(2)
C38H38F2N4O6Zn2
815.46
295(2)
Monoclinic
P21/c
11.2365(6)
8.3087(4)
19.4733(10)
90
93.571(2)
90
Triclinic
̅
P1
8.3006(3)
10.19115(4)
11.3579(4)
81.273(2)
89.629(2)
70.055(2)
954.68(6)
 (°)
γ (°)
V (Å3)
3645(10)
1814.51(16)

Z
4
1
2
ρcalcd (gcm-3)
Crystal size (mm)
1.508
0.18 x 0.17 x 0.08
1.460
0.23 x 0.20 x 0.16
1.493
0.592 × 0.371 ×
0.359
F(000)
1696.0
1.376
6.382 – 56.662
-22/22, -13/13, -29/29
436.0
1.314
2.917 – 27.455
-8/10, -13/14,
14/13
840.0
2.153
9.1 – 130.52
-12/13, -9/9, -22/22
abs coeff (mm-1)
 range (°)
range h,k,l
-
No. total refl.
57447
13313
20669
No. unique refl.
4510
4218
3079
99.5
96.5
99.1
Comp. max (%)
Max/min transmission
Data/Restraints/Parameters
Final R[I>2(I)]
0.781/0.896
4510/0/246
R1 = 0.0439,
wR2 = 0.0939
R1 = 0.0652,
wR2 = 0.1033
1.171
0.810/0.759
4218/0/218
R1= 0.0261,
wR2= 0.0621
R1= 0.0313,
wR2= 0.0647
1.035
0.441/0.462
3079/0/239
R1 = 0.0387,
wR2 = 0.1123
R1 = 0.0417,
wR2 = 0.1147
1.055
R indices (all data)
Goodness of fit / F2
Largest diff. Peak/hole (eÅ-3)
0.550/-0.400
0.331/-0.204
0.830/-0.500
2.4.rac-Lactide polymerization
In a typical experiment for polymerization in melt, a round bottom flask was charged with a stirring
bar, 1.5 g (10.4 mmol) of rac-LA, 22 mg (0.013 mmol, 0.125% mol) of catalyst 5, and 55 mg (0.5
mmol) of benzylalcohol. The reaction mixture was melted at 130 °C with an oil bath and stirred for
4 h. The flask was taken off, cooled to room temperature, and opened in air. An aliquot was
analyzed by 1H NMR spectroscopy for determining the conversion. 0.5 mL of acidic methanol (1.0
M, HCl/MeOH solution) was added in the flask, and the polymer was precipitated with excess
methanol. Then, the supernatant solution was removed with a pipet and the polymer was dried
under vacuum to constant weight. The ratios of rac-lactide, catalyst, benzylalcohol, and reaction
times employed for the various catalytic tests are given in section 3.3 (Table 3).
3. Results and discussions
3.1.Synthesis of ligands and complexes
The synthetic route to the known 1 [38] and new 2 ligand precursors corresponds to a Claisen
condensation between the appropriate 4-substituted acetophenone and ethyl acetate leading to the
formation of the corresponding betadiketone, and subsequent condensation with 2-aminophenol to
generate the desired O,N,O tridentate Schiff base proligands (Scheme 1). This route provided both
compounds in high yields, around 85%. Subsequent synthesis of mononuclear complexes 3 and 4
consists in abstracting two acidic protons of the ligands with an excess of potassium tert-butoxide.

Pyridine is then incorporated as an auxiliary ligand -in slight excess to stabilize tetracoordinated
complexes- before incorporating the Zn(II) salt (Zn(NO3)2x6H2O) (Sheme 1). The observed color
changes indicated reaction progress: the yellow and orange colors of ligands 1 and 2, respectively,
turned intense red upon reaction with t-BuOK, and finally the Zn(ii) complexes 3 and 4 shaded to a
color very similar to that of their respective ligands. Complexes 3 and 4 are isolated as powdered
solids in 66% and 52% yields, respectively. They are soluble in dimethylformamide (DMF),
dimethylsulfoxide (DMSO) and pyridine but are poorly soluble in more common organic solvents
such as dichloromethane, acetonitrile and acetone.
Scheme 1. Synthesis of compounds 1-7

Recrystallization of 4 from a CH2Cl2/pyridine mixture leads to the isolation of the doubly
phenoxide-bridged dimeric specie 5 with the pyridine ligand occupying the fifth coordination site at
the Zn(II) metal center (Scheme 1). Similarly, recrystallization of 3 and 4 from vapor diffusion of
diethyl ether into respective DMF solutions affords isostructural binuclear complexes 6 and 7,
respectively, though with a DMF molecule instead of pyridine as the fifth Zn(II) coordination
ligand (Scheme 1). This ability of Zn(II) to form binuclear complexes has been reported in previous
works [23,31,32,46,47]. Only those three binuclear complexes 5-7 were tested as catalysts in the
ROP of rac-Lactide depicted in this paper (see Section 3.3).
3.2.Compound characterization
1
Mononuclear complexes 3 and 4 were characterized by satisfactory elemental analysis, H NMR
spectroscopy and mass spectrometry as detailed in the experimental section, clearly informing that
they correspond to the proposed structures. Fig. 1 compares the 1H NMR spectra of these complexes
to those of their respective ligands. Spectra of tridentate ligands 1 and 2 recorded in deuterated
chloroform show all proton peaks. Both compounds have fairly similar spectra, with slight
differences in the chemical shifts, due to phenyl ring substitution with MeO- for 1 and F- for 2. The
acceptor character of the fluorine substituent causes an downfield shift of the proton signals (d and
e, Fig. 1). Ligand 2 has greater aromatic proton signal multiplicity: the triplet observed at 6.86 ppm
for compound 1 (g, Fig. 1), appears again for ligand 2 at 6.89 ppm. The signal here is a triplet of
doublet, confirming F nucleus coupling with phenyl ring proton nuclei. In spectra of both 1 and 2,an
acidic N-H proton is observed above 12 ppm, likely due to its intramolecular hydrogen bond with
the carbonyl oxygen.
Fig. 1 shows the 1H NMR spectra of Zn(II) complexes 3 and 4.Unlike their respective ligands, these
were insoluble in deuterated chloroform, so measurements were made in lower concentrations of
deuterated DMSO solutions. Here, all protons were also assigned, largely similar, though with
aromatic proton displacement differences. Three proton signals corresponding to coordinated
pyridine were observed in both compounds (j, k, and l, Fig. 1). Finally, the absence of acidic N-H
protons in both complexes confirms ligand coordination to the metal center through the amino
1
nitrogen atom. The H NMR signals did not present large differences in chemical displacement,
with the only exception in the methyl proton peaks (b, Fig. 1).From complexes to corresponding
ligands, these protons are downfield shifted, passing from 1.67 and 1.77 ppm for 1 and 2, to 2.32

and 2.33 ppm for 3 and 4, respectively. Those chemical shift differences bear testimony to the
coordination of the ligands to the Zn(II) metal ion and formation of rigid structures.
Fig. 1 1H NMR spectra of 1 and 2 obtained in CDCl3; and of 3 and 4 recorded in DMSO-d6.
3.3.X-ray crystallography
The molecular structure of 5 is displayed in Fig. 2 while those of 6 and 7 are presented in Fig. 3.
Selected bond lengths and angles of the first Zn(II) coordination sphere of 5-7 are given in
Table 2. compounds 5, 6 and 7 crystallize in the orthorhombic, triclinic and monoclinic crystal

̅
systems in the centrosymmetric space groups Pbca, P1 and P21/c, respectively. The X-ray
crystal structures of 5–7 indicate that the three complexes are doubly phenoxide-bridged
dimeric species in which each monomeric unit is composed of a pentacoordinated Zn(II) metal
center through a dianionic O,N,O-tridentate Schiff base ligand, a bridging oxygen atom and
either a pyridine (5) or a DMF (6 and 7) molecule. On the other hand, the three dimeric
̅
complexes generate the whole molecular structure related by an inversion center (1), in the
middle of the molecule due to their high molecular symmetry. Moreover, all the compounds
present a slightly distorted square pyramidal geometry (τ5 =0.07, 0.06 and 0.65,
respectively)[48] .
Fig. 2 ORTEP plot of compound 5. Hydrogen atoms are omitted for clarity. Thermal ellipsoids
are drawn with 30% probability.

Fig. 3 ORTEP plots of compounds 6 (above) and 7 (below). Hydrogen atoms are omitted for clarity.
̅ ̅
̅
Thermal ellipsoids are drawn with 30% of probability (i = 푋, 푌, 푍).
All the bond distances and angles (Table 2) are in agreement with those of previously reported
zinc(II) complexes with similar features [49,50] and the formation of five- and six-membered
metallacycles shows distortions similar to that observed for known structurally characterized Schiff
base complexes [37,38,51]. Nevertheless, the metrical parameters measured in the two fused
heterometallacycles are indicative of a delocalization over the entire system.

It is also important to highlight that the distances between apical ligand (Py for compound 5 and,
DMF for compound 6 and 7), present a bond distance slightly larger than other similar compounds
[49,50] . This feature could be responsible for their catalytic response in ring opening
polymerization of rac-lactide, according to its catalytic mechanism [8,25]. Between the three
complexes, there are not major differences in their structural parameters (Table 2). However, the
bond distances in the apical ligand in each compound, allow to infer about the catalytic response
between compounds 5 – 7, due to DMF as ligand, is a weak ligand than Py. This could explain the
greater reactivity that compound 7 presented under mild polymerization conditions, but at the same
time, a lower control in the polydispersity of PLA. These results are discussed in more detail in
section 3.4.
Table 2. Selected Bond distance (Å) and angles (º) of the Zn(II) coordination core for
compounds 5–7.
Compound
5
6
7
Bond distances
Zn(1)-O(1)
Zn(1)-O(2)
Zn(1)-N(1)
Zn(1)-N(2)
Zn(1)-O(3)
Zn(1)-Zn(1)’
1.963(2)
2.004(12)b
2.010(11) / 2.124(11)b
2.024(13)b
1.999(2)
2.090(2) / 2.030(2)a
2.060(2)
2.027(2) / 2.123(14)c
2.013(19)c
---
2.095(2)
---
---
2.005(12)
3.121(3)
2.045(2)
3.117(7)
3.250(2)
Bond angles
O(1)-Zn(1)-L
N(1)-Zn(1)-L
O(2)-Zn(1)-L
N(1)-Zn(1)-O(2)
O(1)-Zn(1)-N(1)
O(1)-Zn(1)-O(2)
Zn(1)-O(2)-Zn(1)’
105.07(10)
100.33(10)
107.06(10)
78.36(9)
94.52(9)
147.84(10)
104.13(9)
95.15(5)
113.27(6)
92.00(2)
80.08(5)
92.49(5)
171.28(5)
98.00(5)
97.05(6)
117.26(7)
89.93(6)
79.86(6)
92.42(6)
171.39(5)
97.78(8)
L: 5=N(2); 6 and 7=O(3)
a
b
c
̅
̅ ̅
X, 1-Y, Z; X, 2-Y, 1-Z; 1-X, 1-Y, 1-Z
3.4.Reactivity studies of complexes 5-7 in ROP of rac-lactide
One of the main objectives of this work was to study the catalytic activity of these three complexes
5-7 in ring opening polymerization to obtain PLA. Table 3 shows the polymerization tests
performed with the three synthesized binuclear complexes. In short, bulk polymerizations in a
melted reaction mixture of monomer rac-LA at 130°C for 4-18 hours and different concentration
ratios of monomer and catalyst were studied. Additionally, benzyl alcohol has been incorporated as

a cocatalyst in some tests, since there are previous reports indicating that different alcohols in low
concentration improve the catalytic activity of some complexes [29]. Table 3 also shows the
influence of these polymerization variables on the degree of conversion and the molecular weight of
the PLA obtained. Fig. 4 shows an example of how 1H NMR characterization allows calculating the
degree of conversion through clear differences in monomer and polymer proton signals. Such
signals can be individually integrated, giving rise to the composition of the reaction mixture.
1
Furthermore, H NMR approximates PLA molecular weight through PLA polymer chain terminal
group proton signals (e and g, Fig. 4). Considering the contribution of their areas in relation to the
rest of the protons in the spectrum, the number of repetitive monomeric units was calculated,
reporting approximate chain length averages (Mn). Synthesized PLA samples were also
characterized by GPC, which, in addition to the average molecular weight, gives chain size
distribution by calculating the polydispersity index (Table 3).
Fig. 4 Example of 1H NMR spectrum of PLA with 87% conversion, obtained with complex 7 as
catalyst and BnOH as cocatalyst (Table 3, Entry 12).

Table 3. ROP of rac-lactides catalyzed by complexes 5, 6, and 7.
b
c
Mn
Mn
[rac-LA
]:[Zn]:[BnOH]
Time
(h)
Conv.a
(%)
c
Entry
Complex
(kg mol-1) (kg mol-
Mw/Mn
1
)
1
2
400:1:0
400:1:20
400:1:0
800:1:0
400:1:0
400:1:20
400:1:0
800:1:0
400:1:0
400:1:20
800:1:0
800:1:20
400:1:0
400:1:20
800:1:0
4
4
69
97
97
95
68
98
98
92
78
97
67
87
97
98
2.2
2.3
3.5
4.9
2.0
4.1
4.0
8.5
2.5
2.5
3.1
3.6
4.8
2.6
1.7
1.7
4.4
6.0
1.5
5.8
4.1
13.3
1.8
1.9
3.0
4.0
5.9
2.4
1.30
1.33
1.38
1.55
1.17
1.60
1.76
1.34
1.28
1.34
1.30
1.52
1.90
1.54
1.59
5
5
5
5
6
6
6
6
7
7
7
7
7
7
3
18
18
4
4
5
6
4
7
18
18
4
8
9
10
11
12
13
14
4
4
4
18
18
15
16
18
18
95
98
3.6
3.6
4.9
4.4
7
7
800:1:20
1.60
Conversion percentage determined by H NMR; b Average molecular weight determined by H NMR;
a
1
1
cAverage molecular weight and polydispersity index determined by GPC calibrated versus polystyrene
standards and corrected by a factor of 0.58 according to literature recommendations [52].
Table 3 shows some general trends of the catalytic behavior of complexes 5-7. After 4 hours of
reaction, no complex is able to generate the highest possible degree of conversion; after 18 hours,
however, or with BnOH as co-catalyst, all conversions reach high values (>90%). Of the three
catalysts studied, complex 7 achieves 78% conversion in 4 hours of reaction, making it the fastest
catalyst under these conditions (Entries 1, 5, and 9).Reaction times of 18 hours provide conversions
of around 98% for all catalysts, similar to results obtained with benzyl alcohol (Entries 2, 6, and
10). On the other hand, reducing catalyst concentration by half ([rac-LA]:[Zn]=800:1) negatively
affects conversion rates, independent of co-catalyst (entries 11 and 12). This is quite expected, due
to the lower concentration of active centers to initiate polymerization.If the same concentration of
catalyst is allowed to react for a longer time, however, conversions can be equally high as in cases
where the concentration of catalyst is higher (entries 4, 8, and 15). Decreasing the catalyst

concentration may affect PLA molecular weight. Indeed, initial catalyst concentrations generally
generated relatively low molecular weights, ranging from 1.7 to 4.4 kg mol-1 (400:1). Thus a
decrease in active polymerization sites should generate longer PLA chains if polymerization is
stable over time.
To discuss the influence of catalysts and reaction conditions on the molecular weight of PLA, it is
necessary to consider some differences of the two methods by which the average molecular weight
(Mn) value has been calculated. Although GPC is one of the most widely used, and considered the
most suitable method for the determination of Mn of polymers, the 1H NMR method also provides a
1
good approximation of this value. Table 3 shows how the H NMR method approximates more
closely to GPC results when molecular weight values are lower. In such cases terminal group proton
contribution is greater, accounting for the majority of integrated signals. In addition, methodology
results are similar for low polydispersity samples because 1H NMR calculations assume equal chain
size. In some cases, the methods differ by less than 10% (entries 11,12,14); in others, more
considerably (30%, entry 8). Nevertheless, increasing or decreasing trends for PLA molecular
weight are of the same respect to the polymerization conditions variation. Thus both methodologies
provide information for catalyst behavior and reaction condition effects on Mn.
The results presented in Table 3 show that Mn increases when the concentration of catalyst
decreases. Catalyst 6 reaches 13.3 kg mol-1 with only a slight increase in polydispersity. This is
remarkable since other Mn increases are accompanied by considerable increases in polydispersity.
Next, as time and conversion rate, PLA chain length also tends to increase, though with different Mn
and polydispersity effects for each complex. For example, decreased concentrations of catalyst 5
increase chain length by up to 200% (entry 4), without seriously affecting polydispersity. This
implies heterogeneous catalyst reactivity: over an extended period of 18 hours, not all active centers
are equally effective, therefore generating chains of different length. On the other hand, and unique
to catalyst 5, Mn can be slightly increased by increasing time without decreasing concentration,
while mostly maintaining polydispersity (entry 3). In this case, a higher catalyst concentration
favors more stable polymerization. The latter behavior could be attributed to the presence of
pyridine as an auxiliary ligand in catalyst 5. Finally, although BnOH as a co-catalyst allows better
conversions, the effect on Mn is negative. In the only case where there is a considerable increase in
Mn, polydispersity is highly increased. In general, it is advisable to reduce concentration of the three
catalysts and extend reaction times.
The three catalysts behave similarly to changes in reaction conditions, e.g., BnOH presence or
different concentrations. That said, differences may be attributable to structural modifications, like

the auxiliary ligand (DMF vs. pyridine) or the nature of the substituents (F vs. MeO). For example,
catalysts 5 and 7, which have fluoride in their structure, generate better conversions at shorter
reaction times, but lower PLA molecular weights, implying that the acceptor effect of fluoride
favors more reactive, less-controlled polymerization. Less reactive catalyst 6 bearing the MeO-
substituent, achieves higher molecular weights with the advantage of maintaining polydispersity.
Finally, the effect of the auxiliary ligand under identical conditions for complexes 5 and 7 (entries 3
and 15) shows very little difference in conversion percentage; that said,at higher Mnvalues, the
DMF catalyst presents an important increase in polydispersity, which does not occur in the case of
pyridine (catalyst 5).
4. Conclusions
Zn(II) binuclear complexes 5, 6, and 7 synthesized via dimerization of their fully characterized
mononuclear precursors 3 and 4 during recrystallization were found to be stable compounds under
environmental conditions, capable of being used as catalysts in the rac-LA polymerization
reactions. They are similar in regards to ROP, with high sensitivity toward the presence of BnOH as
a co-catalyst or higher conversion rates over longer periods of time. On the other hand, PLA with
different characteristics can be synthesized by controlling polymerization conditions (time and
catalyst concentration) in the absence of BnOH. Here, the catalytic behavior is attributed to
structural differences. Complexes with a fluoride substituent were slightly more reactive but had
less control over average molecular weight than the catalyst bearing the donor methoxy group. The
inclusion of pyridine instead of DMF as an auxiliary fifth coordination ligand generates better
control of PLA polydispersity. Finally, the MeO-substituted catalyst generated the highest Mn PLA
when used in low concentrations, though with a reaction time of 18 h and a conversion rate slightly
lower than other catalysts under the same polymerization conditions.
Acknowledgements
The authors thank F. Lambert (CRMPO, Rennes) for helpful assistance with MS measurements.
Financial support from FONDECYT Postdoctoral project 3160673 (D.M.G.), FONDEQUIP
(EQM130154), the Vicerrectoría de Investigación y Estudios Avanzados, Pontificia Universidad
Católica de Valparaíso, Chile (D.M.G. and C.M.) , the CNRS and the Université de Rennes 1 is
gratefully acknowledged. I.B. and J.C. thank FONDEQUIP (EQM 130021) and financial support

from Universidad de Antofagasta for the access to Cambridge Structural Database (CSD), and J.C.
thanks de Universidad de Antofagasta for the Postdoctoral Fellowship.
Appendix A: supplementary information.
CCDC 1862423 (for 5), 1863233 (for 6) and 1862424 (for 7) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.as.uk/data_request/cif
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Binuclear (II) zinc complexes were obtained from dimerization of their
mononuclear precursors with the aim of studying the catalytic activity of
these compounds in the ring-opening polymerization of rac-lactide,
considering the influence of its structural features on the conversion
percentage, molecular weight average and polydispersity of the obtained
PLA.