Journal of Organometallic Chemistry 978 (2022) 122471

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Journal of Organometallic Chemistry

journal homepage: www.elsevier.com/locate/jorganchem

Unsymmetrical ONO-type pincer complexes of palladium(II) containing

amino acid barbiturate derivatives: Synthesis, characterization, and
catalytic applications in Suzuki–Miyaura cross-coupling reaction
Erkan Fırıncı a,∗, Rukiye Fırıncı a, Resul Sevinçek b, Muhittin Aygün b,
Muhammet Emin Günay a
a
Department of Chemistry, Faculty of Science, Aydın Adnan Menderes University, 09010 Aydın, Turkey
b
Department of Physics, Faculty of Science, Dokuz Eylül University, 35160-Buca, Izmir, Turkey

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

Article history: New two tridentate pincer ligands were prepared by the reaction between the selected amino acids and
Received 1 July 2022 1,3-dimethyl barbituric acid. The corresponding Pd(II) complexes were synthesized from the treatment of
Revised 30 July 2022
palladium(II) acetate with the prepared ligands in presence of an ancillary ligand such as pyridine, triph-
Accepted 2 August 2022
enylphosphine, or 1-methylimidazole. All ligands and Pd(II) complexes were characterized by standard
Available online 3 August 2022
spectroscopic and analytical techniques. The crystal and molecular structures of two complexes were de-
Keywords: termined by single-crystal X-ray diffraction revealing a slightly distorted square-planar geometry around
Amino acid the metal center to which the ligand bonded in an ONO-tridentate fashion. The catalytic activities of
ONO-pincer ligand Pd(II) complexes were evaluated in the Suzuki-Miyaura coupling reaction of phenylboronic acid with the
Palladium complexes different aryl halides. They showed good activity for 4-substituted aryl bromide with phenylboronic acid.
Suzuki-Miyaura reaction © 2022 Elsevier B.V. All rights reserved.
X-ray diffraction

1. Introduction Especially, pincer complexes of palladium have attracted great at-

tention due to their high stability and catalytic activity in cross-
Transition metal complexes are still of great interest because coupling reactions [13].
they possess a wide range of medicinal, analytical, and industrial While ECE and ENE (E: N, P, O S) type Pd-pincer complexes de-
applications [1,2]. The efficiency of complexes in the applications rived from the central pyridine or aryl rings are dominantly ex-
is related to their electronic and steric features. The electronic and amined, there are a few studies on the Pd-pincer complexes with-
steric features of metal complexes depend on the metal’s nature out pyridine or aryl backbones [14]. Recently, ONO, ONN, and ONS
and the type of ligands [3]. Palladium complexes have captured type Pd-pincer complexes with Schiff base were synthesized and
the attention of researchers in organometallic chemistry since investigated their catalytic performance on the C–C coupling re-
Wacker’s first example of the homogeneous palladium-catalyzed actions [6,15-19]. In particular, the ONO-type Pd-pincer complexes
reaction in 1959 [4]. Although palladium complexes bearing phos- have been determined to behave as very effective catalysts for
phines or N-heterocyclic carbenes (NHCs) are extensively used as a Suzuki-Miyaura cross-coupling reactions [18,20,21]. Amino acids
catalyst in cross-coupling reactions, their sensitivity to oxygen re- have drawn tremendous attention in coordination chemistry be-
quires an inert atmosphere to carry out the catalytic studies [5–9]. cause tridentate ligands can be prepared from them. Also, they
The researchers have focused on preparing stable Pd complexes for can act as ONO pincer-type ligands. In recent years, amino acid-
catalytic reactions. In this sight, tridentate ligands have a strong based pincer complexes have been reported to show good biologi-
potential because they can strongly attach to the transition met- cal and catalytic efficiencies [18,22-25]. The catalytic activity stud-
als. Additionally, the steric and electronic properties of tridentate ies of Pd-pincer carrying amino acid derivatives on Suzuki-Miyaura
ligands can be easily tuned for the synthesis of new complexes. cross-coupling reactions have been less examined than their bio-
Pincer-type ligands are an important member of the tridentate lig- logical activity studies in the literature [26–30]. These reports in-
and family [10]. Numerous pincer complexes have been reported spired us to prepare amino acid-based Pd-pincer complexes and
after their first examples were published in the late 1970s [11,12]. examine the catalytic applications. We present herein the synthesis
and characterization of new pincer-type ligands from amino acids
and their corresponding palladium(II) complexes. Also, the catalytic
∗
Corresponding author. performance of the ONO-pincer Pd(II) complexes was explored for
E-mail address: efirinci@adu.edu.tr (E. Fırıncı). Suzuki-Miyaura cross-coupling reactions.

https://doi.org/10.1016/j.jorganchem.2022.122471
0022-328X/© 2022 Elsevier B.V. All rights reserved.
E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Table 1
Crystal data and structure refinement parameters of 3b and 4a.

3b 4a

Empirical formula C28 H26 Cl2 N3 O5 PPd C15 H16 N4 O5 Pd

Formula weight 692.79 438.72
Temperature/K 150.00(10) 150.01(10)
Crystal system Triclinic Monoclinic
Space group P-1 P21
a/Å 9.0495(5) 4.7884(3)
b/Å 9.3442(4) 16.4967(11)
c/Å 17.0442(8) 9.7803(6)
α /° 100.149(4) 90
β /° 96.798(4) 94.255(6)
γ /° 96.832(4) 90
Volume/Å3 1394.25(12) 770.44(9)
Z 2 2
ρ calc g/cm3 1.650 1.891
μ/mm-1 0.959 1.242
F(000) 700.0 440.0
Crystal size/mm3 0.388 × 0.29 × 0.195 0.39 × 0.14 × 0.09
Radiation Mo Kα (λ = 0.71073) MoKα (λ = 0.71073)
2 range for data collection/° 6.496 to 52.738 8.358 to 51.436
Index ranges −10 ≤ h ≤ 11, -11 ≤ k ≤ 11, -16 ≤ l ≤ 21 −5 ≤ h ≤ 3, -20 ≤ k ≤ 17, -11 ≤ l ≤ 11
Reflections collected 8290 2472
Independent reflections 5609 [Rint = 0.0253, Rsigma = 0.0496] 2038 [Rint = 0.0251, Rsigma = 0.0592]
Data/restraints/parameters 5609/0/363 2038/4/229
Goodness-of-fit on F2 1.049 1.035
Final R indexes [I>=2σ (I)] R1 = 0.0333, wR2 = 0.0737 R1 = 0.0432, wR2 = 0.1099
Final R indexes [all data] R1 = 0.0393, wR2 = 0.0774 R1 = 0.0514, wR2 = 0.1132

2. Experimental

2.1. Materials and physical measurement

All the solvents (C2H5OH, CH2Cl2, HOAc, DMF, Et2O, IPA,

HC(OEt)3) and chemical reagents (Pd(OAc)2, glycine, L-alanine,
1,3-dimethyl barbituric acid, KOH, Cs2CO3, pyridine, PPh3, 1-
methylimidazole, phenylboronic acid, 2,6-dimethylphenylboronic
acid, 4-bromobenzene, 4-bromotoluen 4-bromoacetophenone, 2-
bromoanisole and 4-chloroacetophenone) were obtained commer-
cially and used as received. Elemental analyses for C, H, and N
were carried out on a LECO CHNS- 932 elemental analyzer by
METU Central Laboratory (Ankara, Turkey). Infrared spectra were
measured with an ATR Spectrum-II, PerkinElmer spectrometer. The
1 H- and 13C NMR spectra were recorded on a Varian 400 spec-

trometer in DMSO–d6 and CDCl3. The residual signals of the sol-

vent were used as references. Melting points were obtained on a
Stuart SMP30 melting point apparatus in open capillary tubes and
were uncorrected.
The single-crystal X-ray diffraction study of 3b and 4a was
performed by w-scan technique, using a Rigaku-Oxford Xcal-
ibur diffractometer with an EOS-CCD area detector operated at
50 kV and 40 mA using graphite-monochromated MoKα radiation
(λ = 0.71073 Å) from an enhance X-ray source with CrysAlis Pro-
software [31]. Data reduction and analytical absorption corrections
were carried out by the CrysAlis Pro-program [32]. The structure
was solved by the Intrinsic Phasing method with the SHELXT and
refined by utilizing the SHELXL program [33,34] incorporated in
the OLEX2 program package [35]. The crystallographic data and re-
finement parameters are given in Table 1. Anisotropic thermal pa- Scheme 1. Synthesis of 1,2.
rameters were applied to all non-hydrogen atoms. All the hydro-
gen atoms were placed using standard geometric models and with
their thermal parameters riding on those of their parent atoms. 100 mL round-bottom flask, and N,N-dimethylformamide/acetic
acid (1/5) was mixed at 60 °C. It was boiled under reflux for
2.2. Synthesis of ligands (1,2) 2 h (Scheme 1). The product was precipitated by adding diethyl
ether (10 mL) after the solution cooled to room temperature. The
1,3-dimethylbarbituric acid (5 mmol), glycine/L-alanine precipitated product was filtered off. It was washed two times
(5 mmol), triethyl orthoformate (7 mmol) was taken into a with diethyl ether and dried under a vacuum.

2
E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Scheme 2. Synthesis of 3 and 4.

2.2.1. Synthesis of 1 (pyridine-o-C), 150.6 (CH=C), 159.1 (C = O), 160.9 (C = O), 161.6
White powder 0.995 g, Yield: 82.6%, m.p.: 278–279 °C. IR (ν (C = O), 181.3 (C = O).
cm−1): 3266, 3001–2652 (br), 1709, 1667, 1651, 1615. Anal. Calc.
for C9H11N3O5: C, 44.82; H, 4.60; N, 17.42; found: C, 44.88; H,
4.52; N, 17.39. 1H NMR (400 MHz, DMSO–d6, δ ): 3.13 (s, 3H, 2.3.2. Synthesis of 3b
NCH3), 3.14 (s, 3H, NCH3), 4.32 (d, J: 6.3 Hz, 2H, HNCH2), 8.21 (d, Yellow powder, 0.333 g, Yield: 78.1%, m.p.: 258–260 °C. IR (ν
J: 14.9 Hz, 1H, C=CH), 10.25 (m, 1H, HNCH), 13.08 (s, 1H, COOH). cm−1): 1700, 1679, 1654, 1629. Anal. Calc. for C27H24N3O5PPd: C,
13C{1H} NMR (100 MHz, DMSO–d6, δ ): 26.8 (NCH3), 27.4 (NCH3), 53.35; H, 3.98; N, 6.91; found: C: 53.41, H, 3.88; N, 6.90. (400 MHz,
49.9 (HNCH2), 90.2 (CH=C), 151.7 (CH=C), 160.5 (C = O), 162.2 DMSO–d6, δ ): 2.34 (s, 3H, NCH3), 3.27 (s, 3H, NCH3), 4.47 (s,
(C = O), 163.7 (C = O), 170.4 (C = O). 2H, NCH2), 7.43–7.47 (m, 6H, PPh3–H), 7.52–7.56 (m, 2H, PPh3–H),
7.59–7.64 (m, 6H, PPh3–H), 8.26–8.30 (dt, J1: 18.0 Hz, J2: 1.4 Hz,
2.2.2. Synthesis of 2 1H, C=CH). 13C{1H} NMR (100 MHz, DMSO–d6, δ ): 27.8 (NCH3),
White powder, 0.100 g, Yield: 78.9%, m.p.: 249–251 °C. IR (ν 28.2 (NCH3), 58.8 (NCH2), 92.2 (CH=C), 127.2, 127.7, 129.0, 129.1,
cm−1 ): 3201, 3002–2688 (br), 1733, 1662, 1655, 1611. Anal. Calc. 131.6, 134.1, 134.3 (PPh3–C), 150.5 (CH=C), 156.1 (C = O), 160.9
for C10 H13 N3 O5 : C, 47.06; H, 5.13; N, 16.46; found: C, 47.15; H, (C = O), 162.9 (C = O), 181.3 (C = O).
5.22; N, 16.49. 1 H NMR (400 MHz, DMSO–d6, δ ): 1.47 (d, J:
6.7 Hz, 3H, CHCH3 ), 3.13 (s, 3H, NCH3 ), 3.14 (s, 3H, NCH3 ), 4.57 2.3.3. Synthesis of 3c
(m, 1H, CHCH3 ), 8.27 (d, J: 14.5 Hz, 1H, C=CH), 10.47 (dd, J1 : White powder, 0.447 g, Yield: 73.5%, m.p.: 235–237 °C.
14.5 Hz, J2 : 7.8 Hz, 1H, HNCH), 13.30 (s, 1H, COOH). 13 C{1 H} NMR IR (ν cm−1): 3133, 1708, 1656, 1637, 1615. Anal. Calc. for
(100 MHz, DMSO–d6, δ ): 18.8 (CHCH3 ), 26.8 (NCH3 ), 27.4 (NCH3 ), C13H15N5O5Pd: C, 36.51; H, 3.53; N, 16.37, found: C: 36.54,
56.1 (CHCH3 ), 90.3 (CH=C), 151.6 (CH=C), 158.5 (C = O), 162.1 H, 3.52; N, 16.09. 1H NMR (400 MHz, DMSO–d6, δ ): 3.12 (s,
(C = O), 163.9 (C = O), 172.5 (C = O). 3H, NCH3), 3.23 (s, 3H, NCH3), 3.75 (s, 3H, imidazole-NCH3),
4.40 (s, 2H, NCH2), 6.86 (s, 1H, imidazole-CH=CH), 7.33 (s, 1H,
2.3. General procedure for the synthesis of Pd-pincer complexes imidazole-CH=CH), 7.78 (s, 1H, imidazole-N=CH–N), 7.79 (s, 1H,
(3a-c,4a-c) C=CH). 13C{1H} NMR (100 MHz, DMSO–d6, δ ): 27.8 (NCH3), 28.8
(NCH3), 38.9 (imidazole-NCH3), 60.6 (NCH2), 92.0 (CH=C), 121.8
After the ligand (1 mmol) was dissolved in 10 mL of ethanol, (imidazole-CH=CH), 125.5 (imidazole-CH=CH), 137.8 (imidazole-
KOH (2 mmol) was added and stirred at room temperature for 2 h. N=CH–N), 149.9 (CH=C), 160.5 (C = O), 161.9 (C = O), 179.5
Pd(OAc)2 (1 mmol) and ancillary ligand (pyridine, triphenylphos- (C = O), 180.2 (C = O).
phine, 1-methylimidazole) (1 mmol) were added to the obtained
solution and stirred at room temperature for 1 day (Scheme 2).
The precipitated Pd-pincer complex was isolated by filtration. It 2.3.4. Synthesis of 4a
was washed with diethyl ether and dried under a vacuum. Pale-yellow powder, 0.380 g, Yield: 86.7%, m.p.: 272–274 °C. IR
(ν cm−1): 1706, 1651, 1623, 1606. Anal. Calc. for C15H16N4O5Pd:
2.3.1. Synthesis of 3a C, 41.06; H, 3.68; N, 12.77; found: C: 41.01, H, 3.63; N, 12.76. 1H
Pale-yellow powder, 0.322 g, Yield: 76.0%, m.p.: 292–294 °C. NMR (400 MHz, DMSO–d6, δ ): 1.44 (d, J: 7.0 Hz, 3H, CHCH3),
IR (ν cm−1 ): 1709, 1666, 1630. Anal. Calc. for C14 H14 N4 O5 Pd: 3.15 (s, 3H, NCH3), 3.26 (s, 3H, NCH3), 4.50 (m, 1H, CHCH3),
C, 39.59; H, 3.32; N, 13.19, found: C: 39.48, H, 3.28; N, 13.15. 7.71 (m, 2H, pyridine-m-H), 7.92 (s, 1H, C=CH), 8.14 (t, J: 7.6 Hz,
1 H NMR (400 MHz, DMSO–d6, δ ): 3.04 (s, 3H, NCH ), 3.14 (s, 1H, pyridine-p-H), 8.47 (d, J: 7.0 Hz, 2H, pyridine-o-H). 13C{1H}
3
3H, NCH3 ), 4.52 (s, 2H, NCH2 ), 7.37–7.69 (m, 2H, pyridine-H), NMR (100 MHz, DMSO–d6, δ ): 21.5 (CHCH3), 27.9 (NCH3), 28.9
7.81 (s, 1H, C=CH), 8.15–8.56 (m, 3H, pyridine-H). 13 C{1 H} NMR (NCH3), 66.6 (CHCH3), 92.4 (CH=C), 126.1 (pyridine-m-C), 140.3
(100 MHz, DMSO–d6, δ ): 27.7 (NCH3 ), 28.7 (NCH3 ), 66.4 (CHCH3 ), (pyridine-p-C), 148.9 (pyridine-o-C), 150.0 (CH=C), 156.0 (C = O),
92.2 (CH=C), 125.9 (pyridine-m-C), 140.2 (pyridine-p-C), 148.7 160.9 (C = O), 161.8 (C = O), 181.5 (C = O).

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E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Fig. 1. Molecular structure of 3b and 4a showing the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. For clarity, H atoms are omitted.

2.3.5. Synthesis of 4b 2, may be attributed to ν (C = O) stretching vibration of the bar-

Yellow powder, 0.367 g, Yield: 81.3%, m.p.: 267–269 °C. IR (ν biturate. All complexes of (3 and 4) FT-IR spectra show absorption
cm−1): 1705, 1681, 1639, 1624. Anal. Calc. for C28H26N3O5PPd: bands in the region 1709–1606 cm−1 for ν (C = O). The FT-IR ab-
C, 54.07; H, 4.21; N, 6.76; found: C: 54.11; H, 4.19; N, 6.72. 1H sorption peaks at 3133 and 3126 cm−1 for 3c, and 4c were as-
NMR (400 MHz, DMSO–d6, δ ): 1.47 (d, J: 7.0 Hz, 3H, CHCH3), signed C–H stretching group on the 1-methylimidazole ring.
2.26 (s, 3H, NCH3), 3.10 (s, 3H, NCH3), 4.47 (m, 1H, CHCH3), 7.56– The NCH3 protons were observed as singlet at δ 3.13 and δ
7.63 (m, 15H, PPh3–H), 8.29 (d, J: 18.0 Hz, 1H, C=CH). 13C{1H} 3.14 ppm for ligands (1 and 2) in 1H NMR spectra. Synthesized lig-
NMR (100 MHz, DMSO–d6, δ ): 21.5 (CHCH3), 27.5 (NCH3), 27.8 ands have two specific peaks vinylic-CH and enamine-NH protons.
(NCH3), 63.1 (CHCH3), 91.7 (CH=C), 127.2, 127.7, 129.3, 131.8, 133.8, The chemical shift of the vinylic-CH showed one doublet peak at δ
133.9 (PPh3–C), 149.9 (CH=C), 159.0 (C = O), 160.5 (C = O), 162.1 8.21 and δ 8.27 ppm, respectively. Enamine NH proton appeared at
(C = O), 183.8 (C = O). δ 10.25 (dd) and δ 10.47 (m) ppm. Enamine NH proton disappeared
in the 1H NMR spectra for complexes (3 and 4). The absence of
the enamine NH proton peaks can be interpreted as a deprotona-
2.3.6. Synthesis of 4c
tion of ligands by Pd(OAc)2. The vinylic carbon atoms were seen
White powder, 0.435 g, Yield: 70.0%, m.p.: 231–233 °C. IR (ν
at δ 151.7 and δ 151.6 ppm, the carbonyl carbons of appeared be-
cm−1): 3126, 1703, 1677, 1617. Anal. Calc. for C14H17N5O5Pd: C,
tween δ 158.0–173.0 ppm for ligands, δ 155.0–184.0 ppm for com-
38.07; H, 3.88; N, 15.85; found: C: 38.04, H, 3.81; N, 15.89. 1H NMR
plexes in the 13C NMR spectrum. The observed signals in the range
(400 MHz, DMSO–d6, δ ): 1.41 (d, J: 7.0 Hz, 3H, CHCH3), 3.14 (s, 3H,
2.26–3.27 ppm were assigned as the NCH3 protons of synthesized
NCH3), 3.25 (s, 3H, NCH3), 3.76 (s, 3H, imidazole-NCH3), 4.40 (q,
complexes (3 and 4). The 1H NMR spectrum of vinylic-CH was ob-
J: 7.0 Hz, 1H, CHCH3), 6.90 (s, 1H, imidazole-CH=CH), 7.36 (s, 1H,
served at δ 7.81, δ 8.26–8.30, δ 7.79, δ 7.92, δ 8.29, and δ 7.91 ppm
imidazole-CH=CH), 7.85 (s, 1H, imidazole-N=CH–N), 7.91 (s, 1H,
for complexes, respectively. The chemical shift of CH carbon was
C=CH). 13C{1H} NMR (100 MHz, DMSO–d6, δ ): 21.3 (CHCH3), 27.8
seen between δ 149.0–151.0 ppm for 3 and 4 in the 13C NMR spec-
(NCH3), 28.8 (NCH3), 34.3 (imidazole-NCH3), 65.7 (CHCH3), 92.2
trum. The FT-IR and NMR data of 1–4 are in good agreement with
(CH=C), 121.9 (imidazole-CH=CH), 125.7 (imidazole-CH=CH), 137.9
the reported similar compounds [36–38].
(imidazole-N=CH–N), 150.0 (CH=C), 155.3 (C = O), 160.7 (C = O),
161.9 (C = O), 182.2 (C = O).
3.2. Structural studies

3. Results and discussion X-ray quality crystals were obtained by layering a

dichloromethane solution with diethyl ether and storage at
3.1. Synthesis and characterization of ligands and complexes room temperature. The single-crystal XRD studies proved that
the barbiturate ligands are coordinated to the palladium ion
The ONO tridentate ligands bearing amino acid (1,2) and their through ONO in a tridentate fashion. ORTEP diagrams of 3b and
pincer type Pd(II) complexes (3,4) were synthesized and character- 4a, demonstrated in Figs. 1 and 2, show ONO pincer type of ligand
ized by elemental analysis, 1H-, 13C NMR, and FT-IR spectroscopy. coordinated with central metal palladium ion via the carbonyl
The FT-IR spectra of the observed bands at 3266 and 3201 cm−1 oxygen of barbiturate, enamine nitrogen, and carboxylate oxygen
can be assigned to enamine stretching vibration ν (N–H) for 1, and of amino acid moiety, each forming five- and six-membered
2, respectively. The observed broad bands between 30 0 0 and 2690 chelate rings. The fourth sites of Pd ion in 3b and 4a are oc-
cm−1 were assigned stretching vibration of OH group on amino cupied by triphenylphosphine and pyridine as the ancillary
acid in the spectra of 1, and 2, respectively. The ν (O–H) stretch- ligand, respectively. Complex 3b was crystallized in the P-1 space
ing frequencies of 3 and 4 disappeared in the region between group in the triclinic crystal system. The trans angles of the
30 02/30 01 and 2688/2652 cm−1 when the ligand was attached to complex 3b O(2)-Pd(1)-O(3) and N(1)-Pd(1)-P(1) are 174.60(8)o
the metal center in the FT-IR spectrum. The bands at 1709, 1667, and 177.09(7)o respectively. Selected geometric parameters are
1651, and 1615 cm−1 for 1, 1733, 1662 1655, and 1611 cm−1 for given in Table 2. The 3b crystal contains the solvent molecule

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E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

these H-bonding interactions, π - π type interactions are also ob-

served between Cg3…Cg4b , Cg3…Cg5c , Cg4…Cg3c and Cg5…Cg3b
with the Cg…Cg distances of 3.880(6) Å, 3.995(6) Å, 3.879(6) Å
and 3.996(6) Å, respectively. (The Cg descriptions are as follows
for 4a: Cg3:Pd1/O3/C13/C10/C9/N2; Cg4:N3/C12/N4/C11/C10/C13;
Cg5:N1/C1/C2/C3/C4/C5. The symmetry codes are b :1 + x,y,z;
c :−1 + x,y,z).

In 3b and 4a, metal centers are in slightly distorted square pla-

nar geometry with tridentate ONO ligand. The four-coordinate ge-
ometry indexes (τ 4) of 3b and 4a are 0.060 and 0.058, respectively
[39]. The selected bond lengths and angles confirmed the square
planar geometry around the central metal palladium with slightly
distortion. Distortion is caused by the presence of the dibasic tri-
dentate enamine barbiturate ligands. The maximum deviation from
the coordination plane of 3b is N1 with 0.060 Å, and of 4a is O2
with −0.029 Å. The geometric parameters of complexes 3b and 4a
are in good agreement with the reported ONO-pincer Pd(II) com-
plexes containing triphenylphosphine and pyridine as ancillary lig-
ands [15,17,18,29,40,41].

3.3. Catalytic activity of complexes

Fig. 2. Packing diagram of 3b. Intra- and inter-molecular weak interactions are
shown as dotted lines. Cl…π and π …π interactions are drawn as thin lines.
Initially, catalytic studies were performed upon the Suzuki-
Table 2 Miyaura coupling reaction choosing 4-bromoacetophenone and
Selected bond lengths (Å), bond angles (o ) and torsion angles (o ) phenylboronic acid as a model substrate in the presence of com-
of the complexes 3b and 4a. plex 3a for optimization studies. The base, solvent, temperature
Bond Lengths (Å) 3b 4a and catalyst loading were studied and optimized (Table 4). Accord-
ing to our optimization studies, IPA and Cs2 CO3 were determined
Pd1-P1 2.2966(7) Pd1-N1 2.047(8)
Pd1-N1 2.001(2) Pd1-N2 1.939(8)
as the best solvent and base at 80 º C.
Pd1-O2 1.9976(19) Pd1-O2 1.978(9) The catalyst loading tests showed the best yield obtained by
Pd1-O3 2.0087(19) Pd1-O3 2.010(9) utilizing 1 mmol of complex 3a. Reducing catalyst loading from 0.1
O2-C2 1.311(3) O2-C6 1.284(13) to 0.01 mol% under the optimized conditions resulted in low yields
C2-C3 1.529(4) C6-C7 1.525(15)
(Table 4, entry 3,10,11).
C3-N1 1.467(3) N2-C7 1.452(16)
N1-C4 1.288(3) N2-C9 1.299(16) We examined the activity of 3 and 4, in the Suzuki-Miyaura
C4-C5 1.423(4) C9-C10 1.39(2) cross-coupling reaction under the optimized conditions. During the
C5-C6 1.406(4) C10-C13 1.409(15) course of performing experiments on the catalytic dehalogena-
O3-C6 1.284(3) O3-C13 1.259(13) tion of aryl bromides with 3 and 4 (0.1 mol%) using 2-propanol
Angles (o ) 3b 4a
O2-Pd1-P1 95.47(6) O2-Pd1-N1 92.3(3)
(3 mL) as the solvent and Cs2 CO3 as the base (1.5 Equiv.) We
O2-Pd1-N1 83.43(8) O2-Pd1-N2 83.0(4) obtained very high yields of products at 1 h, 80 °C (Table 5).
O2-Pd1-O3 174.61(8) O2-Pd1-O3 176.2(3) The results showed that ONO pincer-type Pd(II) complexes ex-
N1-Pd1-P1 177.08(7) N1-Pd1-N2 175.3(5) hibit excellent activity at low catalyst loadings with 4-substituted
N1-Pd1-O3 92.62(9) N2-Pd1-O3 94.0(4)
aryl bromides. 4-substituted aryl bromides bearing either electron-
P1-Pd1-O3 88.65(6) N1-Pd1-O3 90.7(4)
withdrawing or electron-donating groups provided the correspond-
ing cross-coupling products in good yields. 4-bromoacetophenone,
including the electron-withdrawing group, was successfully cou-
(dichloromethane), which connect the adjacent complex with pled with phenylboronic acid providing around 81–92% yield in
the C–H…O type weak interactions (Fig. 2). In addition to these 1 h (Table 5, entries 13–18). The coupling reaction of bromoben-
C–H…O type interactions, the crystal structure of 3b is stabilized zene with phenylboronic acid afforded between 86 and 98% yield
by C–H… π and C–Cl…π interactions shown in Fig. 3. Geometric of the product in 1 h (Table 5, entries 1–6). The reaction of phenyl-
details are given in Table 3. Besides, two π …π type interac- boronic acid with including electron-rich group, 4-bromotoluen,
tions are observed between Cg1…Cg2a and Cg2…Cg1a with the provided the biaryl products with more than 80% yield (Table 5,
Cg…Cg distance of 3.6837(15) Å. (Cg1:Pd1/N1/O3/C4/C5/C6 and entries 7–12). The coupling reaction of phenylboronic acid with
Cg2:N2/N3/C5/C6/C8/C10 and the symmetry code a: 1-x,1-y,1-z). 2-bromoanisole was performed in presence of catalyst 3a and re-
Considering these Cl…π , π …π and C–H…O type interactions, 1D sulted in a very low yield at 1 h and 24 h (Table 5, entry 20).
chain is constructed along the b-axis (Fig. 3). Similarly, 2,6-dimethylphenylboronic acid was converted by cata-
Complex 4a was crystallized in the P21 space group in the lyst 3a to the corresponding product with a low yield due to the
monoclinic crystal system. Selected bond lengths are given in steric hindrance of aryl boronic acid (Table 5, entry 21).
Table 2. The trans angles of the complex 4a O(2)-Pd(1)-O(3) and Complex 3a has higher yields as compared to other pre-
N(1)-Pd(1)-N(2) are 176.30(3)o and 175.30(4)o respectively. Con- pared complexes in the Suzuki-Miyaura reaction for phenylboronic
sidering the crystal stability of 4a, one intra- and five inter- acid and the selected 4-substituted aryl bromide (Table 5). Un-
molecular H-bonding interactions are observed (in Fig. 3). In- fortunately, 2-substituted substrates resulted in low yields with
teractions via H2, H3 and H4 atoms generate a 2D polymeric complex 3a due to the steric hindrance (Table 5, entry 20,21).
sheet. Besides, 1D chains are generated along an-axis via C7- In addition, the activity of the catalysts in the cross-coupling
H7… O1 weak interactions, and along b-axis via C15-H15C…O1 reaction of 4-substituted aryl chloride was tested. 3a and 4-
interactions. All these interactions generate a 3D polymeric struc- chloroacetophenone were selected as catalyst and model substrates
ture. All geometric details are given in Table 3. In addition to for the catalytic test. However, the catalyst (3a) was less effective

5
E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Fig. 3. Packing diagram of 4a. (a) Intra- and inter-molecular weak interactions are shown as dotted lines. Adjacent complexes bounded by H-bonding are shown in solid
colors. (b) inter-molecular π …π interactions. Cg…Cg distances are also given.

Table 3
Geometric parameters of intra- and intermolecular interactions of 3b and 4a. Symmetry codes i :x, −1 + y, z;
ii
:2-x,1/2 + y,1-z; iii :2 + x,y,1 + z; iv :2-x, −1/2 + y,1-z; v :−1 + x,y,z; vi :1-x,1/2 + y,1-z.

Structure d(D–H) /d(D-X) d(H…A)/d(X…Cg) d(D…A)/ d(D…Cg) D-H…A/ d-X…Cg

3b C1-H1A … O1i 0.97 2.28 3.206(4) 160

3b C22-H22…O2 0.93 2.54 3.138(3) 122
3b C1-Cl2…Cg1 1.762(4) 3.499(1) 3.645(4) 94.7(1)
3b C1-Cl1…Cg2 1.752(4) 3.418(2) 3.654(4) 97.8(1)
4a C2-H2…O1ii 0.95 2.56 3.256(18) 131
4a C3-H3…O4iii 0.95 2.33 3.267(16) 170
4a C4-H4…O5iv 0.95 2.58 3.428(18) 149
4a C5-H5…O2 0.95 2.25 2.888(2) 123
4a C7-H7…O1v 1.00 2.45 3.412(14) 162
4a C15H15C…O1vi 0.98 2.60 3.568(16) 171

Table 4
Optimization of reaction conditions for the Suzuki-Miyaura coupling reactiona .

.
− 1 e
Entry Cat. Load. (mol%) Solvent Base Yield (%)b , c TOF (h )

1 0.1 IPA Na2 CO3 27 270

2 0.1 IPA K2 CO3 58 580
3 0.1 IPA Cs2 CO3 92 920
4 0.1 IPA NaOH 61 610
5 0.1 IPA KOH 70 700
6 0.1 EtOH Cs2 CO3 65 650
7 0.1 PhMe Cs2 CO3 22 220
8 0.1 H2 O Cs2 CO3 Trace –
9 0.1 IPA Cs2 CO3 42d 420
10 0.05 IPA Cs2 CO3 61 1220
11 0.01 IPA Cs2 CO3 48 4800
a
Reagents: an aryl bromide (0.50 mmol), PhB(OH)2 (0.75 mmol), Cs2 CO3 (1.50 mmol), diethylene glycol di-n–butyl ether (0.3 mmol, internal standard),
catalyst (3a, 0.1 mol%), and 2-propanol (3.0 mL).
b
Yields based on the aryl halide and average of two runs.
c
All reactions were followed by GC.
d
Room temperature.
e
Turnover Frequency (TOF): Moles of desired product formed/moles of catalyst/ time.

6
E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Table 5
The catalytic activity of 3 and 4 for the coupling of aryl halide and phenylboronic acida .

.
− 1 g
Entry R1 R2 X Cat. Yield (%)b , c TOF (h )

1 H H Br 3a 97 970
2 3b 98 980
3 3c 98 980
4 4a 88 880
5 4b 86 860
6 4c 91 910
7 4- H Br 3a 94 940
8 CH3 3b 82 820
9 3c 91 910
10 4a 86 860
11 4b 84 840
12 4c 88 880
13 4- H Br 3a 92 920
14 COCH3 3b 81 810
15 3c 89 890
16 4a 84 840
17 4b 83 830
18 4c 86 860
19d 4-COCH3 H Cl 3a 12 120
20 2–OCH3 H Br 20 (30)e 200 (300)
21 4-COCH3 2,6-CH3 2 (54)e 20 (540)
22f 4-COCH3 H 91 910
a
Reagents: an aryl bromide (0.50 mmol), PhB(OH)2 (0.75 mmol), Cs2 CO3 (1.50 mmol), diethylene glycol di-n–butyl ether (0.3 mmol, internal standard),
catalyst (0.1 mol%), and 2-propanol (3.0 mL).
b
Yields based on the aryl halide and average of two runs.
c
All reactions were followed by GC.
d
Reagents: 4-chloroacetophenone (0.50 mmol), PhB(OH)2 (0.75 mmol), Cs2 CO3 (1.50 mmol), diethylene glycol di-n–butyl ether (0.3 mmol, internal standard),
catalyst (0.1 mol%), and 2-propanol (3.0 mL).
e
80 ºC, 24 h.
f
In the presence of excess Hg (Hg:Pd = 300:1).
g
Turnover Frequency (TOF): Moles of desired product formed/moles of catalyst/ time.

for coupling 4-aryl chloride. As a result, activity (using 1 mmol% pose, 4-bromoacetophenone and phenylboronic acid as a model
catalyst) was acceptable for activated 4-substituted aryl bromides, substrate with complex 3a (0.1 mol%) using 2-propanol (3 mL) as
but the activity for deactivated substrates was low (Table 5, entry the solvent and Cs2 CO3 as the base (1.5 Equiv.) in the presence
19). On the other hand, the obtained catalytic results can be eval- of excess mercury. The catalytic efficiency of 3a did not change in
uated the efficacy of Pd-ONO pincer complexes slightly increases presence of excess mercury (Table 5, entry 22). The test indicated
when using pyridine and 1-methylimidazole as the ancillary ligand it is a homogeneous catalyst [42].
in the Suzuki-Miyaura reaction. Presumably, the steric hindrance
of triphenylphosphine decreases the catalytic activity of Pd com-
plexes. 4. Conclusions
We compared our complexes with the similar previously re-
ported ONO Pd-pincer complexes in the literature. A series of un- In conclusion, two new ONO-type pincer ligands bearing glycine
usual pincer-like-ONO Pd(II) complexes bearing amino acid was (1)/L-alanine (2) and their corresponding Pd(II) complexes with
prepared and evaluated their catalytic properties for C–C coupling pyridine, triphenylphosphine, and 1-methylimidazole as ancillary
reactions [29]. 4-acetylbiphenyl was obtained with the conversa- ligands were synthesized and characterized by standard spectro-
tion of 41% by loading 0.1 mol% catalyst at 24 h and 40 ºC. Com- scopic methods. The crystal and molecular structures of 3b and 4a
plexes 3 and 4 have better activity at 1 h and 80 ºC (Table 5, were proved by single-crystal X-ray diffraction. The X-ray diffrac-
entries 13–18). In another related study, the catalytic activities of tion studies showed that the ligands are coordinated to the metal
unsymmetrical ONO-type Pd(II)-Schiff base complexes were exam- center as the ONO-type pincer ligands with an ancillary ligand.
ined for C–C coupling reactions [15] and their TOF values were These complexes have a slightly distorted square-planar geometry
found to be 192, 188, 192 h − 1 for the coupling products of the re- around the Pd(II) center. The catalytic activity of all complexes was
action of 4-bromobenzene, 4-bromotoluene, 4-bromoacetophenone studied in the Suzuki-Miyaura coupling reaction at mild reaction
with phenylboronic acid, respectively. Our catalytic studies showed conditions. They reached good yields at 1 h and 80 ºC. Complex
that catalysts 3 and 4 have higher TOF values than the given liter- 3a acts as the best catalyst in the Suzuki-Miyaura coupling reac-
ature (Table 5, entry 1–18). tion of phenylboronic acid with different 4-substituted aryl bro-
mides. The obtained data from catalytic studies exhibit that the
3.4. Mercury poising test Pd(II) complexes containing N-donor ancillary ligand have slightly
higher activity than those containing P-donor. Further, ONO-pincer
The mercury poising test was aimed to confirm whether the Pd(II) complexes will be prepared and employed as a catalyst in
catalyst is homogeneous or heterogeneous. A homogeneous cata- different reactions to understand the effect of pincer and ancillary
lyst is not affected in the presence of mercury [42]. For this pur- ligands.

7
E. Fırıncı, R. Fırıncı, R. Sevinçek et al. Journal of Organometallic Chemistry 978 (2022) 122471

Declaration of Competing Interest [12] V.G. Koten, K. Timmer, J.G. Noltes, A.L. Spek, Novel type of Pt–C interaction
and a model for the final stage in reductive elimination processes involv-
ing C–C coupling at Pt; synthesis and molecular geometry of [1, N, N -η-
The authors declare that they have no known competing finan- 2, 6-bis{(dimethylamino)methyl}-toluene]iodoplatinum(II) tetrafluoroborate, J.
cial interests or personal relationships that could have appeared to Chem. Soc., Chem. Commun. 6 (1978) 250–252, doi:10.1039/C39780 0 0 0250.
influence the work reported in this paper. [13] L. González-Sebastián, D. Morales-Morales, Cross-coupling reactions catalysed
by palladium pincer complexes. A review of recent advances, J. Organomet.
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Data availability [14] M.A.W. Lawrence, K.A. Green, P.N. Nelson, S.C. Lorraine, Review: pincer ligands-
Tunable, versatile and applicable, Polyhedron 143 (2018) 11–17, doi:10.1016/j.
The authors do not have permission to share data. poly.2017.08.017.
[15] B. Agrahari, S. Layek Anuradha, R. Ganguly, D.D. Pathak, Synthesis, crystal
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Acknowledgments 354, doi:10.1016/j.ica.2017.11.018.
[16] S.N. Shukla, P. Gaur, S.S. Bagri, R. Mehrotra, B. Chaurasia, M.L. Raidas, Pd(II)
This work was supported by the “Scientific Research Project complexes with ONN pincer ligand: tailored synthesis, characterization, DFT,
and catalytic activity toward the Suzuki-Miyaura reaction, J. Mol. Struct. 1225
Unit (BAP) of Aydın Adnan Menderes University” (Project No: FEF- (2021) 129071, doi:10.1016/j.molstruc.2020.129071.
20013). Also, the authors thank the X-ray Laboratory, Faculty of [17] H. Qian, S. Yu, L. Song, T. Zhang, Z. Yin, F. Zhao, J. Yang, C. Wang, ONO pincer
Science, Dokuz Eylül University, for use of the Oxford-Rigaku Xcal- palladium (II) complexes featuring furoylhydrazone ligands: synthesis, char-
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Supplementary material associated with this article can be ladium(II) Complexes: catalytic Applications in Suzuki–Miyaura Reaction and
Allylation of Aldehydes, ChemistrySelect 4 (2019) 7246–7259, doi:10.1002/slct.
found, in the online version, at doi:10.1016/j.jorganchem.2022. 201900946.
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