Zn(II)-to-Cu(II) transmetalation in an amide functionalized complex and catalytic applications in styrene oxidation and nitroaldol coupling

Article abstract of DOI:10.3390/molecules25112644

The mononuclear zinc(II) complex cis-[ZnL2(H2O)2] (1; L = 4-(pyridin-3- ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of 1 in a mixture of DMF-H2O solution containing a slight excess of Cu(NO3)2 × 3H2Oa transmetalation reaction occurred affording the related copper(II) complex trans-[CuL2(H2O)2] (2). The structures of the compounds were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism, an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties. H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks. The transmetalation was confirmed by SEM-EDS analysis. Moreover, the thermodynamic feasibility of the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities of 1 and 2 for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were investigated. The copper(II) compound 2 acts as heterogeneous catalyst for the microwave-assisted oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99percent) benzaldehyde up to 66percent of conversion and with a turnover frequency (TOF) of 132 h-1. The zinc(II) complex 1 is the most active catalyst (up to 87percent yield) towards the nitroaldol (Henry) coupling reaction between benzaldehyde and nitro-methane or -ethane to afford the corresponding β-nitro alcohols. The reaction of benzaldehyde with nitroethane in the presence of 1 produced 2-nitro-1-phenylpropanol in the syn and the anti diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34).

Full text of DOI:10.3390/molecules25112644

molecules
Article
Zn(II)-to-Cu(II) Transmetalation in an Amide
Functionalized Complex and Catalytic Applications
in Styrene Oxidation and Nitroaldol Coupling
Anup Paul * , Luísa M. D. R. S. Martins * , Anirban Karmakar, Maxim L. Kuznetsov
M. Fátima C. Guedes da Silva * and Armando J. L. Pombeiro *
,
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal;
anirban.karmakar@tecnico.ulisboa.pt (A.K.); max@mail.ist.utl.pt (M.L.K.)
* Correspondence: anuppaul@tecnico.ulisboa.pt (A.P.); luisammartins@tecnico.ulisboa.pt (L.M.D.R.S.M.);
fatima.guedes@tecnico.ulisboa.pt (M.F.C.G.d.S.); pombeiro@tecnico.ulisboa.pt (A.J.L.P.)
ꢀꢁꢂꢀꢃꢄꢅꢆꢇ
Academic Editors: Diego A. Alonso and Natalia V. Belkova
Received: 1 May 2020; Accepted: 4 June 2020; Published: 6 June 2020
ꢀꢁꢂꢃꢄꢅꢆ
Abstract:
ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of
DMF-H2O solution containing a slight excess of Cu(NO3)2
affording the related copper(II) complex trans-[CuL2(H2O)2] (
The mononuclear zinc(II) complex cis-[ZnL2(H2O)2]
(
1
;
L
=
4-(pyridin-3-
1
in a mixture of
×
3H2O a transmetalation reaction occurred
). The structures of the compounds
2
were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism,
an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties.
H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks.
The transmetalation was confirmed by SEM–EDS analysis. Moreover, the thermodynamic feasibility of
the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities
of
investigated. The copper(II) compound
oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99%) benzaldehyde
up to 66% of conversion and with a turnover frequency (TOF) of 132 h−1. The zinc(II) complex
is
the most active catalyst (up to 87% yield) towards the nitroaldol (Henry) coupling reaction between
benzaldehyde and nitro-methane or -ethane to afford the corresponding -nitro alcohols. The reaction
of benzaldehyde with nitroethane in the presence of produced 2-nitro-1-phenylpropanol in the syn
1
and
2
for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were
2
acts as heterogeneous catalyst for the microwave-assisted
1
β
1
and the anti diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34).
Keywords: amide functionalized; transmetalation; DFT calculations; oxidation of styrene; nitroaldol
1. Introduction
Transmetalation is commonly associated with an organometallic compound and involves a
transfer of organic groups or ligands from one metal to another [1–3]. It thus provides a common and
convenient method for preparing various organo-transition metal complexes, which are otherwise
difficult to synthesize via direct metal-ligand self-assembly. Such phenomenon is well documented
and has expanded to other types of materials [4–11]. The process usually proceeds through either
“direct exchange”, where the incoming metal does not alter the topology of the frameworks or through
“disruptive exchange” in which the geometry of the transmetalation complex differs from the original
structure as a result of the metal exchange.
Several metal-organic frameworks (MOFs) have been employed in transmetalation to synthesize
novel materials which would otherwise be difficult to obtain [12
–
15]. The role of ligands in the process
cannot be ruled out.
Molecules 2020, 25, 2644; doi:10.3390/molecules25112644
www.mdpi.com/journal/molecules

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Previously, the presence of a carboxylate and a pyridyl moieties in the ligand framework of
(4-(pyridin-3-ylcarbamoyl)benzoate) was used for the synthesis of MOFs or coordination polymers
(CPs) by Luo et al. [16]. The presence of a carboxylate and pyridyl moieties was used for the
synthesis of MOFs or coordination polymers (CPs) but, in the present study, we failed to generate such
types of compounds through hydro/solvothermal reaction using a zinc salt. Instead, unexpectedly a
mononuclear molecular zinc(II) complex was obtained, being susceptible to undergo transmetalation
with copper(II) (see below).
In pursuing our interest on the synthesis of metal-based complexes for application in catalysis,
we have been using amide functionalized ligands primarily because the amide backbone in the ligand
framework can provide a basic environment and facilitate the catalytic reaction [17–20]. Furthermore,
the presence of multiple coordinating sites in the ligand skeleton can provide favorable stretched
frameworks having a large surface area, also advantageous for catalysis.
Concerning a catalytic application, the preparation of benzaldehyde is an important process as
this compound is a valuable chemical for perfumery, dyestuff, pharmaceutical and agro-chemical
industries [21
benzaldehyde is produced by catalytic partial oxidation of toluene or by hydrolysis of benzylidene
chloride [26 27]. Both processes present low yields, harsh conditions and a significant generation of
–25]. Although it can be obtained by oxidation of benzyl alcohol, traditionally
,
waste. Therefore, there is a need to find more environmentally friendly processes using green oxidation
agents (e.g., hydrogen peroxide) and heterogeneous catalyst systems.
On the other hand, the nitroaldol (Henry) reaction is also relevant, being widely used to build C–C
bonds by the formation of β
-nitro alcohols (from the Csp3–Csp2 coupling reaction between a nitroalkane
and a carbonyl compound), which are important synthetic precursors. This reaction can be carried out
with homogeneous and heterogeneous catalysts, as well as with alkali metal hydroxides, alkoxides or
amines [28
this kind of reaction [17
–
31]. We have already reported a variety of homogeneous and heterogeneous catalysts for
18 32 35]. Despite several progresses, good enantio- and diastereoselectivity
,
, –
is rarely achieved. Thus, also for this reaction, a need for improved catalytic systems remains.
Herein, we present the synthesis and structural analysis of the new mononuclear complex of zinc(II)
cis-[ZnL2(H2O)2] (
trans-[CuL2(H2O)2] (
modification led to the formation of compound
Complexes and are shown to catalyze the oxidation of styrene towards benzaldehyde and the
Henry reaction of an aldehyde with a nitro alkane to form a -nitro alcohol. The mononuclear Cu(II)
complex acts as a heterogeneous catalyst for the microwave-assisted selective oxidation of styrene to
1
, L = 4-(pyridin-3-ylcarbamoyl)benzoate) and of the derived copper(II) compound
). was synthesized by hydrothermal reaction, whereas its post-synthetic
through transmetalation, which is irreversible.
2
1
2
1
2
β
2
benzaldehyde, whereas the Zn(II) complex
1 converts successfully benzaldehyde into β-nitro alcohols.
2. Experimental Section
Materials and Methods
Solvents were dried and distilled before their use. Reagents were obtained from commercial
sources and used without further purification. Methyl-4-(chlorocarbonyl)benzoate was prepared
following a procedure reported earlier [36]. FT-IR spectra were recorded on a Bruker Vertex 70 (Bruker
1
Corporation, Ettlingen, Germany) instrument in KBr pellets. H (300 MHz) and 13C (75.45 MHz) NMR
spectra were obtained at room temperature (RT) on a Bruker Avance II + 300 (UltraShield™Magnet,
Rheinstetten, Germany) spectrometer using tetramethylsilane [Si(CH3)4] as an internal reference.
Carbon, hydrogen, and nitrogen elemental analyses were carried out by the Microanalytical Service
of the Instituto Superior T
in a D8 Advance Bruker AXS (Bragg Brentano geometry, Bruker, Madison, WI, USA) theta-2-theta
diffractometer, with copper radiation (Cu K = 1.5406 Å) and a secondary monochromator, operated
écnico, Lisboa, Portugal. Powder X-ray diffraction (PXRD) was conducted
α, λ
at 40 kV and 40 mA. Flat plate configuration was used, and the typical data collection range was
between 5◦ and 40◦. Thermal properties were performed using a PerkinElmer Instrument system

Molecules 2020, 25, 2644
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◦
(STA6000, Perkin-Elmer, Boston, MA, USA) at a heating rate of 10 C min−1 under a dinitrogen
atmosphere flow rate of 30 mL/min. The synthesized compounds were characterized in terms of
structural and optical properties by scanning electron microscopy (SEM) and energy-dispersive X-ray
spectroscopy (EDX) using a scanning electron microscope JEOL 7001 F (JEOL, Akishima, Tokyo, Japan)
with Oxford light elements EDX detector.
3. Synthesis and Characterization
3.1. Synthesis of 4-(Pyridin-3-Ylcarbamoyl)Benzoic Acid (HL)
The pro-ligand was synthesized according to a reported procedure [16,36].
3.2. Synthesis of cis-[ZnL2(H2O)2] (1)
Zn(NO3)2 6H2O (40 mg; 0.134 mmol) dissolved in 1 mL of water was added to a 1 mL DMF
·
solution of HL (33 mg; 0.135 mmol). The mixture was sealed in an 8 mL glass vessel and heated at
75 ◦C for 24 h. Upon standing at room temperature for two days, crystals were formed, isolated by
filtration, washed with DMF followed by deionized water, and dried in air. Yield: 70% (based on Zn).
Anal. Calcd for C26H22ZnN4O8: C, 53.49; H, 3.80; N, 9.60. Found: C, 53.53; H, 3.83; N, 9.62. IR (KBr,
cm−1): 3320 (bs), 1648 (s), 1593 (m), 1584 (s), 1482 (s), 1408 (m), 1385 (m), 1295 (m), 1234 (m), 1018 (m),
901 (m), 865 (w), 841 (w), 799 (w), 701 (w).
3.3. Synthesis of trans-[CuL2(H2O)2] (2)
An aqueous solution of Cu(NO3)2
×
3H2O (25 mg; 0.103 mmol) was added to the synthesized
complex (50 mg; 0.085 mmol) soaked in DMF:H2O (1:1, v/v) and left undisturbed at room temperature.
1
Deep blue crystals formed after two days, were collected by filtration, washed with DMF, deionized
water, methanol, and dried in air. Yield: 60% (based on Cu). Anal. Calcd for C26H22CuN4O8: C, 53.49;
H, 3.80; N, 9.60. Found: C, 53.50; H, 3.85; N, 9.62. IR (KBr, cm−1): 3288 (bs), 1653 (s), 1631 (w), 1593 (w),
1530 (s), 1483 (w), 1386 (m), 1375 (w), 1294 (m), 1335(w), 1105 (w), 1020 (w), 799 (w), 736 (m), 665 (m).
4. Crystal Structure Determination
Single crystals of
1 and 2 were leapt in cryo-oil, mounted in a nylon loop and measured at room
temperature. Intensity data were collected using a Bruker APEX-II PHOTON 100 diffractometer (Bruker,
Madison, WI, USA) with graphite monochromated Mo-Kα (λ = 0.71069) radiation. Data were collected
using phi and omega scans of 0.5◦ per frame, and a full sphere of data was obtained. Cell parameters
were retrieved using Bruker SMART [37] software and refined using Bruker SAINT [37] on all the
observed reflections. Absorption corrections were applied using SADABS [38]. Structures were solved
by direct methods by using the SIR97 program and refined with SHELX-2014/7 [39,40]. Calculations
were performed using the WinGX System–Version 2014.1 [41]. The hydrogen atoms were inserted in
calculated positions and included in the refinement using the riding-model approximation; Uiso (H)
were defined as 1.2 Ueq of the parent carbon atoms for phenyl residues. The water hydrogen atoms
were found in the difference Fourier map and were included in the refinement using the riding-model
approximation with the Uiso(H) defined as 1.5 Ueq of the parent O-atom. PLATON/SQUEEZE [42
]
was used to correct the data. Crystallographic data are summarized in Table 1 and selected hydrogen
bonding interactions are presented in Table S1. CCDC 2000481-2000482 contains 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.ac.uk/data_request/cif.

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Table 1. Crystal data and structure refinement details for compounds 1 and 2.
Identification Name
Formulae
Mol. wt.
1
C26H22N4O8Zn
583.84
2
C26H22N4O8Cu
582.01
Crystal system
Space group
Temperature/K
Wavelength/Å
a/Å
Monoclinic
C2/c
Monoclinic
P21/c
296
296
0.71073
32.201(2)
5.1266(3)
16.0629(11)
119.367(2)
2311.0(3)
4
0.71073
7.9726(4)
5.1600(3)
28.6218(14)
91.262(2)
1177.18(11)
2
b/Å
c/Å
β/◦
V/Å3
Z
Density/Mgm−3
Abs. Coeff./mm−1
F(000)
1.678
1.642
1.127
0.991
1200
598
Refl. collected
R(int)
22855
15987
0.0658
0.0263
Refl. Obs/unique
Max. θ/◦
2118/1838
25.392
2160/2118
25.412
−38 <= h <= 38
−6 <= k <= 6
−19 <= l <= 19
−9 <= h <= 9
−6 <= k <= 6
−34 <= l <= 34
Ranges (h, k, l)
Complete to θ (%)
N◦ Parameters
R1 [I > 2σ(I)]
wR2 [I > 2σ(I)]
R1 [all data]
wR2 [all data]
GOF
99.8
99.3
186
187
0.0290
0.0618
0.0386
0.0649
1.114
0.0701
0.1588
0.0710
0.1591
1.355
5. Computational Details
The full geometry optimization of all structures was carried out at the DFT level of theory by
using the M06 functional [43] with the help of the Gaussian 09 program package [44]. No symmetry
operations were applied. The standard basis set 6-31G* was applied for all atoms. Solvent effects were
taken into account in single-point calculations based on gas phase geometry using the “density-based”
solvation model (SMD) solvation model with water and DMF selected as solvents [45]. The 6-311+G**
and Def2-TZVP basis sets were applied in these calculations for non-metal and metal atoms, respectively.
The solvent effect for the 1:1 mixture of water and DMF was approximated as the average value
obtained for pure water and DMF solvents. The optimization of complex
at the SMD(H2O)-B3LYP/6-31+G* and SMD(H2O)- B97XD/Def2-TZVP levels of theory. The Cartesian
atomic coordinates of the calculated equilibrium structures are presented in Table S2.
1 was additionally performed
ω

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The Hessian matrix was calculated analytically for the optimized structures to prove the location
of correct minima (no imaginary frequencies) and to estimate the thermodynamic parameters, with the
latter calculated at 25 ◦C. The Gibbs free energies in solution, Gs, discussed in the text were obtained
as Gs = Es(6-311 + G**/Def2-TZVP) – Eg(6-31G*) + Gg(6-31G*), where Es and Eg are total energies in
solution and gas phase and Gg is gas phase Gibbs free energy obtained using the indicated basis set.
6. Catalytic Studies
Typical oxidation of styrene was performed under microwave irradiation (10 W) in a focused
microwave Anton Paar Monowave 300 (Anton Paar GmbH, Graz, Austria) discover reactor fitted with
a rotational system and an IR temperature detector. A 10 mL capacity cylindrical Pyrex tube with a
13 mm internal diameter was used: catalyst (10
µmol), the substrate (1.0 mmol), hydrogen peroxide
(30% w/w aq. sol., 2.0 mmol), 1.5 mL of acetonitrile and 100
µL of chlorobenzene as internal standard
were stirred at 80 ◦C for the desired reaction time. During the reaction, small aliquots were taken,
cooled down, centrifuged (to separate the catalyst from the sample), and analyzed by GC–MS using the
internal standard method for quantification. GC–MS analyses were conducted at a Perkin-Elmer Clarus
600 C (Shelton, CT, USA) apparatus, using He as the carrier gas, with an ionization voltage of 70 eV
and an SGE BPX5 column (30 m
×
0.25 mm
×
0.25 µm). The comparison of the products retention times
with those of known reference compounds enabled their identification. Moreover, their mass spectra
fragmentation patterns were compared with those obtained from the National Institute of Standards
and Technology (NIST) spectral library of the computer software of the spectrometer. The values of
conversion considered result from two concordant assays. Blank reactions were performed for the best
conditions in the absence of complexes
1 or 2 and confirmed that almost no oxidation occurs. In some
runs under the optimized conditions, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO, 1.0 mmol) was
added to the initial reaction mixture as a radical scavenger.
The recyclability of complex
2 was examined, by recovering it by centrifugation after the reaction
being cooled down, washing with ethanol, and drying overnight. A new cycle was run with the
recovered catalyst by addition of new typical portions of all other reagents. After completion of the
reaction, the products were analyzed as above-mentioned.
The experiments for the Henry reaction were carried out in a glass reactor. A mixture of the
nitroalkane (1.5 mmol), benzaldehyde (0.5 mmol), catalyst
1 (50 µmol) and 3 mL of solvent (deionized
water, methanol, dichloromethane, dichloroethane, THF, or acetonitrile) was stirred up to 24 h at
room temperature to 60 ◦C. After the desired reaction time, the solution was extracted with diethyl
ether (3
filtered off. The diethyl ether was removed in vacuo and the organic residue was analyzed by 1H NMR
spectrometry, in CDCl3, for quantification of the formed -nitro alcohols (as no other products were
detected). The anti:syn diastereoisomer ratio of 1-phenyl-2-nitropropanol was determined taking into
×
5 mL), the combined extracts dried over anhydrous Na2SO4, and then the mixture was
β
account the vicinal coupling constants values between the α-O–C–H and the α-N–C–H protons for the
isomers: anti, J = 7–9 Hz; syn, J = 3.2–4 Hz) [46,47].
7. Results and Discussion
Syntheses and Characterization
The pro-ligand HL was prepared according to the reported modified procedure [16]. Compound
1
was synthesized by the hydrothermal reaction between Zn(NO3)2.6H2O and HL in a DMF:H2O solvent
mixture (Scheme 1 and experimental section for synthetic details). The transmetalation reaction to
afford
2
was carried out by soaking crystals of
1 in a DMF:H2O (1:1, v/v) solvent mixture containing a
slight excess of aqueous Cu(NO3)2
days (Figure 1). Both compounds were characterized by elemental analysis, IR, SEM–EDS and single
×
3H2O and leaving it undisturbed at room temperature for two
crystal X-ray diffraction analyses. It is worthy to mention here that we failed the attempts to achieve
the direct synthesis of the transmetalated Cu(II) complex 2 by deprotonating the pro-ligand HL with

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a base, such as KOH, NaOH or NH4OH, and in situ reaction with a copper(II) salt like Cu(NO3)2
3H2O or CuCl2 × 2H2O, at room temperature or heating in methanol or in a DMF:H2O mixture.
×
Scheme 1. Syntheses of compounds 1 and 2.
Figure 1. Conversion of 1 to 2.
The FT-IR spectrum of HL displays a peak at ca. 1705 cm−1 assigned to the asymmetric stretching
vibration of the carboxyl group which, upon coordination to the metal cations shifts to the lower
frequency values of 1648 cm−1 (in 1) and 1653 cm−1 (in 2) (Figure S1).
8. Crystal Structure Analysis
The crystal structures of
are presented in Figure 2. Crystallographic data of the compounds
1
and
2
were determined by single-crystal X-ray diffraction analysis and
and are presented in Table 1 and
1
2
hydrogen bond contacts are detailed in Table S1 (Supplementary Materials).
Figure 2. Crystal structures of compounds 1 and 2.
The asymmetric units of the compounds include one metal ion (Zn2+ in
1 2),
or Cu2+ in
one deprotonated L− ligand binding the cations through chelating (in
1) or monodentate (in
2)
carboxylate moieties, and one water molecule (Figure 2). Symmetry expansion reveals mononuclear

Molecules 2020, 25, 2644
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complexes where the water ligands are in mutual cis (in
1
) or trans (in
2
) position. In view of the
constraints derived from the chelating mode of L− in
1
the six-coordinate geometry is better described
as trigonal prismatic with the angle between the least-square planes of the carboxylate groups being
of 78.06◦. In
, the environment around the metal cation can be envisaged as square planar but
2
the long-range interaction between Cu1 and O2 or O20-carboxylate atoms (Cu1···O2/O20 2.606 Å),
being shorter than the sum of the van der Waals radii of Cu (1.40 Å) and O (1.52 Å), can be considered
as giving rise to a highly distorted octahedral geometry. The Zn-O and Cu-O bond distances are in
the range of 2.0197(16)-2.2020(15) Å and 1.955(4)-1.968(3) Å, respectively. The N2 and N20 atoms are
uncoordinated, displaying the syn orientation in 1 and the anti in 2 (Figure 2).
Both compounds are involved in intermolecular H-interaction (Table S1) where the water ligands
act as donors to an O2 and the N2 atoms of vicinal complex molecules (donor···acceptor distances
in the 2.667(6)–2.722(2) Å range;
∠
D
−
H
···A between 151(6) and 168(2) ◦); the N1, in turn, donates to
the O3 atoms, such contacts being less intense than the previous ones (donor···acceptor distances and
D
−
H
···A angles of 3.006(3) Å and 168(3)◦ in
1 2). Resulting from such
, and 3.013(6) Å and 159(6)◦ in
interactions infinite two-dimensional (2D) networks of
the (10-1) or the (100) planes, respectively.
1
or
2
are generated (Figure 3) spreading along
(A)
(B)
Figure 3. Hydrogen bonded networks of compounds 1(A) and 2(B).
9. DFT Calculations
In order to understand the thermodynamic feasibility of the conversion of
transmetalation, DFT calculations were carried out. The DFT calculations with various functionals
and basis sets (gas-M06/6-31G*, SMD(H2O)-B3LYP/6-31+G*, and SMD(H2O)- B97XD/def2-TZVP)
indicated that in both gas and liquid phases the structure of the Zn complex corresponds to
1
to 2 through
ω
1
a distorted tetrahedral coordination sphere with both 4-(pyridin-3-ylcarbamoyl)benzoate ligands
being monodentate (the observed long range Zn-O interaction of the chelating carboxylate groups is
discarded) (Figure 4). Therefore, the structure of complex
1 in the solid state is controlled by crystal
packing effects, first of all by multiple intermolecular interactions described above.

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Figure 4. Equilibrium structures of 1, trans-2 and cis-2.
In accord with the calculations, the experimentally isolated trans-isomer of
2
is more stable
than the corresponding cis-isomer in all water, DMF, and 1:1 water/DMF mixture by 1.6, 2.1 and
1.8 kcal/mol, respectively. The coordination sphere in both optimized structures trans-2 and cis-2
deviates significantly from the square planar configuration with the trans-O–Cu–O angles of 148–158◦.
The carbonyl groups of the ligands form intramolecular H-bonds with coordinated water molecules.
The calculated Gibbs free energy of reaction (1) in the 1:1 water/DMF mixture is
significantly negative ( 12.7 kcal/mol) indicating thermodynamic preference of the transmetalation
−
observed experimentally.
1 + [Cu(H2O)6]2+ → trans-2 + [Zn(H2O)6]2+
(1)
10. Conversion of 1 into 2
The conversion of
During such conversion process, no loss in crystal quality was observed as evidenced by SEM analysis
(inset of Figure 6) as well as by X-ray (see above). The complete conversion of to was validated by
SEM–EDS method (Figure 6). Figure 7 presents the PXRD patterns of and both calculated from their
1 into 2 was evidenced by the color change from colorless to blue (Figure 5).
1
2
1
2
crystal structures and experimentally obtained from the bulk materials, with undeniable resemblance.
Figure 5. Conversion of crystals of 1 to 2, indicating the nature of crystallinity.

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Figure 6. EDS of
1 (A) and 2 (B), showing the complete transformation. Inset shows SEM images of 1
and 2, respectively.
Figure 7. Simulated and experimental PXRD patterns of 1 (A) and 2 (B).
The recurrent attempted synthesis and isolation of
and Cu(NO3)2 3H2O were unsuccessful. Moreover, by soaking crystals of
v/v) solvent mixture and subsequent addition of an aqueous solution containing a molar excess of
Zn(NO3)2 6H2O, no transmetalation reaction took place even after more than a month, showing
the irreversibility of the process on account of the stronger coordination of the ligand to Cu(II) in
comparison with Zn(II). Furthermore, to know if Zn(II) in could be replaced by any other transition
to conversion
2
by hydrothermal reaction between HL
×
2
in a DMF:H2O (1:1,
×
1
metal ion, apart from Cu(II), analogous procedures to that mentioned above for the
1
2
were followed using salts of Mn2+, Co2+, Ni2+, Pb2+ and Cd2+, but no transmetalation was observed
on the basis of EDS analyses (Figure S2), thus, disclosing a curious selectivity towards Cu(II).
11. Catalytic Oxidation of Styrene to Benzaldehyde
Both complexes
1 and 2 were tested for the peroxidative oxidation of styrene. Complex 1 was
not active as a catalyst, since the styrene conversion obtained in its presence was similar to the one

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obtained in blank tests (without any metal catalyst). On the contrary, the copper complex
2 was
successfully tested as a heterogeneous catalyst for the oxidation of styrene by aqueous hydrogen
peroxide, in acetonitrile, yielding selectively (>99%) benzaldehyde (Scheme 2a) under optimized
reaction conditions (microwave irradiation, 80 ◦C, 30 min., 600 rpm, 10 W, noxidant/nsubstrate = 2) up to
66% of conversion and a turnover frequency (moles of product per mole of catalyst per unit of time,
TOF) of 132 h−1
.
Scheme 2.
(a) Microwave-assisted peroxidative oxidation of styrene to benzaldehyde catalyzed by
trans-[CuL2(H2O)2] (
2
); ( ) Nitroaldol (Henry) coupling of benzaldehyde with nitroalkanes (R = H or
b
Me) catalyzed by cis-[ZnL2(H2O)2] (1).
When a decrease in the selectivity for benzaldehyde was found (higher oxidant to styrene molar
ratios, noxidant/nsubstrate
≥
4), although being the major product, the formation of 1-phenylethane-1,2-diol
(up to 23%) was detected. This can suggest that the mechanism for styrene oxidation is initiated
by the Cu-assisted formation of oxygen-centered radicals (hydroxyl and peroxyl, similar to Fenton
chemistry) which oxidize styrene, what is also suggested by the reaction inhibition upon addition of the
radical scavenger 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to the reaction mixture. Moreover, the
epoxide product was not detected, neither acetophenone nor phenylacetaldehyde (from isomerization
of the epoxide).
Besides, an increase in the microwave irradiation time led to the formation of benzoic acid by
overoxidation of benzaldehyde. In fact, if the desired product would be benzoic acid, full conversion
of styrene could be obtained performing the reaction under MW irradiation during 2 h at 80 ◦C with
an increased amount of hydrogen peroxide. Higher temperatures than 80 ◦C were not tested due to
safety reasons.
The recyclability of complex
2 was examined by recovering it through centrifugation (see
Experimental). Although a slight color change was detected for the recovered catalyst, a new cycle was
run with it by addition of new typical portions of all other reagents. Unfortunately, the catalytic activity
of recovered
its reuse.
2 for the second cycle was significantly lower (up to 17% conversion) what prevented
12. Catalytic Benzaldehyde Nitroaldol C-C Coupling
Complex showed a good activity as a heterogeneous catalyst for the Henry coupling reaction of
benzaldehyde with nitroalkanes yielding -nitro alcohols (Scheme 2b) up to 87% conversion under
optimized reaction conditions (24 h at 60 ◦C in MeOH, benzaldehyde: nitroalkane 1:3 and 10 mol% of
vs. benzaldehyde). Moreover, acceptable values of syn:anti selectivity for the diastereoisomers of
1
β
1
1-phenyl-2-nitropropanol, formed by the nitroaldol coupling using nitroethane, were achieved (up to
66:34 syn:anti), with superior selectivity for the syn isomer. The efficiency of the nitroaldol coupling was
shown to be dependent on the solvent: protic solvents (e.g., water or methanol) led to higher yields of
β
-nitro alcohols than aprotic ones (e.g., acetonitrile or THF) (see Figure 8 for 2-nitro-1-phenylethanol).
With the Cu(II) complex as a catalyst, only 32 to 68% benzaldehyde conversions were achieved
after 24 h at 60 ◦C. Following previous studies [18
48 51], the reaction mechanism should involve
metal-assisted (upon coordination) deprotonation of nitroalkane to produce the nitronate species and
2
,
–
activation of benzaldehyde for its electrophilic attack to the nitronate. Therefore, the Zn(II) complex
1
acts more efficiently as a Lewis acid for the aforementioned activation process than its related Cu(II) 2.

Molecules 2020, 25, 2644
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100
90
80
70
60
50
40
30
20
10
0
methanol
water
dichloromethane dichloroethane
acetonitrile tetrahydrofuran
Figure 8. Effect of the solvent type on the yield of the product of the Henry coupling of benzaldehyde
with nitromethane catalyzed by cis-[ZnL2(H2O)2] (1).
Under solvent-free conditions, a significant decrease on the
observed (19% after 24 h at 60 ◦C, with benzaldehyde: nitroalkene 1:3 and 10 mol% of
benzaldehyde). Besides, the reaction does not show any progression in the absence of . The recyclability
β-nitro alcohol production was
1
vs.
1
of complex 1 was impaired by its decomposition during its recovering from the reaction mixture.
13. Conclusions
The mononuclear Zn(II) complex cis-[ZnL2(H2O)2] (
reaction using 4-(pyridin-3-ylcarbamoyl)benzoic acid (HL) as the ligand source, and can be irreversibly
transmetalated to the Cu(II) analogue trans-[CuL2(H2O)2] ( ). The thermodynamic feasibility of
transmetalation is evidenced by DFT studies. The catalytic activity of and were tested for oxidation
and for CC-coupling reactions. Compound with the redox active Cu(II) site acts as heterogeneous
catalyst for the microwave-assisted selective oxidation of styrene to benzaldehyde by aqueous hydrogen
peroxide. In contrast, compound with the strong Lewis acid Zn(II) site was found to be an active
catalyst towards the nitroaldol (Henry) reaction between benzaldehyde and nitroalkanes to afford
the corresponding -nitro alcohols. Further, the reaction of benzaldehyde with nitroethane in the
presence of produced 2-nitro-1-phenylpropanol in the syn and the anti diastereoisomeric forms, with
1) was synthesized through hydrothermal
2
1
2
2
1
β
1
a considerable higher selectivity towards the syn isomer.
Supplementary Materials: The following are available online, Figure S1. IR spectra of HL, 1 and 2, Figure S2.
EDS of the samples to identify any transformation of the metal ions using Pb(II) (A) Co(II) (B), Cd(II) (C), Mn(II)
(D), Ni(II) (E) salts, Table S1. Hydrogen bond interactions (Å, ◦) in compounds 1 and 2, Table S2. Cartesian atomic
coordinates of the calculated equilibrium structures of 1 and 2.
Author Contributions: Conceptualization, A.P.; Formal analysis, A.K.; Funding acquisition, A.J.L.P.; Investigation,
A.P. and L.M.D.R.S.M.; Methodology, A.P.; Project administration, A.P. and L.M.D.R.S.M.; Software, M.L.K. and
M.F.C.G.d.S.; Supervision, A.J.L.P.; Writing—original draft, A.P., L.M.D.R.S.M. and M.L.K.; Writing—review &
editing, A.P., M.F.C.G.d.S. and A.J.L.P. All authors have read and agreed to the published version of the manuscript.
Funding: This work has been partially supported by the Fundação para a Ciência e a Tecnologia (FCT), Portugal,
through projects UIDB/00100/2020 of Centro de Quimica Estrutural, and PTDC/QEQ-ERQ/1648/2014. The authors
A.P., A.K., and M.L.K. are grateful to the FCT and IST, Portugal, for financial support through “DL/57/2017” and
the CEEC Institutional program (Contracts no. IST-ID/197/2019, IST-ID/107/2018 and IST-ID/295/2019). The authors
also acknowledge the Portuguese NMR Network (IST-UL Centre) for access to the NMR facility.
Conflicts of Interest: The authors declare no conflict of interest.

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