Ruthenium(II) complexes derived from 2-phenylthiazoline-4-carboxylic acid: Structure and catalytic activity for transfer hydrogenation reaction

Article abstract of DOI:10.1002/aoc.3442

Piano-stool ([(p-cymene)Ru(thz)Cl], 2) and six-coordinated ([Ru(thz)₂(PPh₃)₂], 3) ruthenium complexes derived from 2-phenylthiazoline-4-carboxylic acid (Hthz, 1) were synthesized for the first time, and fully characterized using conventional methods. Also, the molecular structure of complex 3 was determined using X-ray analysis. These complexes were evaluated as catalysts for transfer hydrogenation of carbonyl compounds in the presence of isopropyl alcohol and KO^tBu. Complex 2 was found to be more active than 3 in transfer hydrogenation.

Full text of DOI:10.1002/aoc.3442

Full paper
Received: 5 October 2015
Revised: 21 December 2015
Accepted: 24 December 2015
Published online in Wiley Online Library: 21 March 2016
(wileyonlinelibrary.com) DOI 10.1002/aoc.3442
Ruthenium(II) complexes derived from
2-phenylthiazoline-4-carboxylic acid:
structure and catalytic activity for transfer
hydrogenation reaction
Serpil Denizaltıa*, Betül Şenb, Aytaç Gürhan Gökçeb and Bekir Çetinkayaa
Piano-stool ([(p-cymene)Ru(thz)Cl], 2) and six-coordinated ([Ru(thz)2(PPh3)2], 3) ruthenium complexes derived from 2-
phenylthiazoline-4-carboxylic acid (Hthz, 1) were synthesized for the first time, and fully characterized using conventional
methods. Also, the molecular structure of complex 3 was determined using X-ray analysis. These complexes were evaluated as
catalysts for transfer hydrogenation of carbonyl compounds in the presence of isopropyl alcohol and KOtBu. Complex 2 was found
to be more active than 3 in transfer hydrogenation. Copyright © 2016 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web site.
Keywords: ruthenium complex; thiazoline; transfer hydrogenation
used as received. 2-Phenyl-4,5-dihydrothiazole-4-carboxylic acid (1)
Introduction
was prepared according to previous literature.[10] Fourier transform
Transition metal-catalysed transfer hydrogenation (TH) of carbonyl
compounds is one of the most important reactions in the pharma-
ceutical and chemical industries.[1] Whereas direct hydrogenation
of unsaturated compounds is more widely applied, TH is a powerful
alternative in view of its easy handling, the ready availability of
hydrogen donor, low cost of reducing agents and safety.[1,2] Over
the last few decades, just a few studies have been reported of the
catalytic activities of amino carboxylate–transition metal complexes
for TH reaction.[3] Among these complexes, the cyclic amino carbox-
ylate proline ligand gave the best results. On the other hand, metal
complexes of carboxylate ligands such as picolinic acid,[4] proline,[5]
quinoline or isoquinoline carboxylic acid,[6] bipyridine carboxylic
acid[7] and thiazole or thiazolidine carboxylic acid[8] are known and
they have been investigated for their luminescence and structural
properties and their biological activities. Also, several ruthenium or
iridium carboxylate complexes have been synthesized and success-
fully applied as catalysts for organic reactions.[9] However, to the
best of our knowledge, there is no report concerning both the
synthesis and the use of thiazoline carboxylate ligands in TH
reaction. In the study reported here, two new thiazoline carboxylate
complexes of ruthenium(II) were synthesized with a view to
applying them for TH reaction of carbonyl compounds.
infrared (IR) spectra were recorded with a PerkinElmer Spectrum
1
100 series spectrometer. H NMR (400 MHz), 13C NMR (100 MHz)
and 31P NMR (161.9 MHz) spectra were measured using a Varian
AS 400 Mercury spectrometer with CDCl3 as the solvent and
tetramethylsilane was used as the internal standard. All coupling
constants (J values) were measured in hertz (Hz). Elemental analyses
were performed with a PerkinElmer PE 2400 elemental analyser.
Synthesis of complex 2
To a solution of 1 (0.1 g, 0.48 mmol) and sodium carbonate (0.051 g,
0.48 mmol) in dry CH2Cl2 (10 ml) was added [RuCl2(p-cymene)]2
(0.148 g, 0.24 mmol). The mixture was stirred overnight at room
temperature. The solution was filtered and then concentrated in
vacuo. The product was recrystallized from CH2Cl2–Et2O.
Yield 43%; m.p. 202–204°C (dec.). IR (ν, cmÀ1): 1651 (νCO). 1H NMR
(δ, ppm): 1.18 (d, 3 H, J = 7.2 Hz, p-cymene-CH(CH3)2, maj.); 1.22
(d, 3 H, J = 7.2 Hz, p-cymene-CH(CH3)2, maj.); 1.23 (d, 3 H,
J = 7.2 Hz, p-cymene-CH(CH3)2, min.); 1.25 (d, 3 H, J = 7.2 Hz, p-
cymene-CH(CH3)2, min.); 2.04 (s, 3 H, p-cymene-CH3, min.); 2.22 (s,
6 H, p-cymene-CH3, maj.); 2.69–2.79 (m, 2 H, p-cymene-CH, maj.;
min.); 3.46–3.65 (m, 4 H, CH2, maj.;min.); 4.43 (d, 2 H, J = 5.6 Hz, p-
cymene-Ar-H, min.); 4.58 (d, 2 H, J = 5.6 Hz, p-cymene-Ar-H, min.);
Experimental
General considerations
*
Correspondence to: Serpil Denizaltı, Ege University, Department of Chemistry,
35100, Bornova-İzmir, Turkey. E-mail: serpil.denizalti@ege.edu.tr
Reactions involving air-sensitive components were performed
under argon atmosphere and using high-vacuum line techniques.
Dichloromethane was distilled under argon atmosphere from
P2O5. All reagents were purchased from commercial sources and
a Ege University, Department of Chemistry, 35100, Bornova-İzmir, Turkey
b Dokuz Eylül University, Department of Physics, 35160, Buca-İzmir, Turkey
Appl. Organometal. Chem. 2016, 30, 373–377
Copyright © 2016 John Wiley & Sons, Ltd.

S. Denizaltı et al.
4.62–4.72 (m, 1 H, CH, min.); 4.86–4.95 (m, 1 H, CH, maj.); 4.96–5.03
(d, 2 H, J = 5.6 Hz, p-cymene-Ar-H, maj.); 5.32 (d, 2 H, J = 5.6 Hz,
information. CCDC 1409243 contains the supplementary crystallo-
graphic data for 3. These data can be obtained free of charge from
the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.
uk/data_request/cif.
p-cymene-Ar-H, maj.); 7.53–7.99 (m, 10 H, Ar-H, maj.; min.). 13
C
NMR (δ, ppm): 18.7 (p-cymene-CH3, min.); 18.8 (p-cymene-CH3,
maj.); 21.9, 22.5 (p-cymene-CH(CH3)2, maj.); 21.8, 22.8 (p-cymene-
CH(CH3)2, min.); 30.7, 30.9 (p-cymene-CH, maj.; min.); 34.1, 35.8
(CH2S, maj.; min.); 79.1, 80.2 (CH, maj., min.); 79.8, 80.1, (p-cymene-
Ar-C, min.); 79.8, 85.1 (p-cymene-Ar-C, maj.); 97.9, 100.3, 102.2,
103.2, 127.1, 128.1, 128.5, 129.1, 129.6, 131.3, 132.9, 133.1 (Ar-C,
min., maj.); 175.1, 176.2 (C N, min., maj.), 178.9, 179.3 (CO, maj.,
min.). Anal. Calcd for C20H22ClNO2RuS (476.98) (%): C, 50.36; H,
4.65; N, 2.94. Found (%): C, 50.35; H, 4.63; N, 2.93.
Results and discussion
Synthesis and characterization of compounds
Compound 1 was synthesized from cysteine, according to a previ-
ously published procedure.[10] When 1 was treated with the metal
precursors [RuCl2(p-cymene)]2 or [RuCl2(PPh3)3] in the presence of
a base complexes 2 and 3 were obtained as red solids scheme 1.
The synthesized ruthenium complexes were fully characterized using
standard NMR techniques. The 1H NMR spectrum of complex 2
Synthesis of complex 3
A solution of 1 (0.1 g, 0.48 mmol) and RuCl2(PPh3)3 (0.23 g, 0.24 mmol)
in MeOH (100 ml) was refluxed for 0.5 h under argon atmosphere.
Then, NEt3 (0.2 ml, 1.9 mmol) was added and the solution was
refluxed for another 4 h. After the solution had cooled to room
temperature, MeOH was removed. The residue was purified using
silica gel column chromatography with elution by toluene–CH3CN
(4:1). The complex was crystallized using layer diffusion with
CH2Cl2–Et2O solvent system.
1
Yield 35%; m.p. 182–185°C (dec.). IR (ν, cmÀ1): 1634 (νCO). H
NMR (δ, ppm): 1.20 (dd, 2 H, J = 11.6 Hz, CH2); 2.93 (dd, 2 H,
J = 11.6 Hz, CH2); 4.49 (dd, 1 H, J = 12.0 Hz, CH); 6.55 (d, 4 H,
J = 7.2 Hz, Ar-H); 7.10–7.44 (m, 36 H, Ar-H). 13C NMR (δ, ppm): 32.4,
82.7, 127.7, 127.8, 127.9, 128.0, 129.0, 129.2, 129.6, 131.4, 178.2,
178.8. 31P NMR (δ, ppm): 37.2. Anal. Calcd for C56H46N2O4P2RuS2
(1038.12) (%): C, 64.79; H, 4.47; N, 2.70. Found (%): C, 64.76; H,
4.46; N, 2.68.
Scheme 1. Synthesis of thiazoline carboxylate ruthenium complexes (2, 3).
General procedure for catalytic TH reactions
shows two sets of signals (1.8:1 ratio) at room temperature, which in-
dicate the complex 2 isolated forms a mixture of two diastereomers.
The 13C NMR spectra of the complexes (2 and 3) show C=N and C=O
resonances at around 175.1–178.2 and 178.9–179.3 ppm, respec-
tively. This is consistent with the N,O-chelating character of the
carboxylate ligand.
The six-coordinated 18-electron complex 3 may exist in five differ-
ent geometric isomeric forms. The 31P NMR spectrum of 3 displays a
single resonance at 37.2 ppm, which indicates that phosphorus
atoms are magnetically equivalent.[16] It is also known that com-
plexes bearing the Ru(PPh3)2 moiety tend to be in cis position in
order to achieve a better dπ–dπ interaction.[17] However, these facts
do not allow us to distinguish two possibilities, where the N or O
atoms are trans to each other (3′ versus 3). Therefore, an X-ray study
was carried out and the collected data for 3 unequivocally confirm
the proposed structures.
A two-necked flask was charged with the catalyst (1 mol%) and
ketone or aldehyde (1 mmol) and dissolved in 5 ml of isopropyl
alcohol (IPA). Then, KOtBu (1 mmol) was added. The solution was
heated at 82°C. After 6 h, the reaction mixture was cooled to room
temperature. The solvent was removed and the residue was
dissolved in hexane–ethyl acetate (1:1) mixture and filtered over a
pad of silica. The yields were determined from 1H NMR spectra.
X-ray diffraction study
The molecular structure of 3 was determined using single-
crystal X-ray diffraction. Single-crystal data were collected at
293(2) K using the ω-scan technique with an Agilent Xcalibur
diffractometer with an Eos CCD area detector using graphite-
monochromated Mo Kα radiation (λ = 0.71073 Å) from an en-
hanced X-ray source. Data collection, cell refinement and data
reduction were performed using the CrysAlisPro program.[11] Solu-
tion, refinement and analysis of the structures were done using
the OLEX2 system.[12] The crystal structures were solved by the di-
rect method using SHELXS-97[13] and refined by the full-matrix
least-squares method based on F2 against all reflections using
SHELXL-97.[13] All non-hydrogen atoms were refined anisotropi-
cally. For complex 3, the carbon-bound hydrogen atoms were re-
fined using a riding model approximation, with C H = 0.93–0.97 Å
and with Uiso(H) = 1.2Ueq(C). Geometrical calculations were per-
formed using PLATON.[14] The figures were made using ORTEP[15]
and PLATON.[14] A summary of the crystal data, experimental de-
tails and refinement results for metal complex 3 is in the supporting
Structural studies
The ruthenium atom of complex 3 is in a distorted octahedral envi-
ronment with cis-triphenylphosphine ligands (Fig. 1). The P–Ru–P
angle is 98.32(2)°, comparable to that in other cis-triphenylphosphine
complexes reported in the literature, the values ranging
between 95.53(4)° and 99.28(2)°.[18,19] Both of the 4,5-
dihydrothiazole-4-carboxylate ligands are bidentate; each contrib-
utes an O atom and one of its two N atoms to coordinate the central
metal. The O atoms are trans to each other, whereas the N atom do-
nors are trans to the P atoms. The two bite angles of the bidentate
chelate ligands are nearly the same: 78.33(1)° for O1–Ru1–N1 and
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2016, 30, 373–377

Thiazoline carboxylate complexes
Table 2. TH of acetophenone using complexes 2 and 3
Entry
Catalyst
Base (mol%)
Yield (%)a
1
2
2
2
3
3
3
KOH (10)
KOH (20)
KOtBu (10)
KOtBu (10)
KOtBu (40)
KOtBu (100)
41
96
2
3
82
4
99
5b
6c
>99
>99
Reaction conditions: 1 mmol substrate, 1 mol% catalyst, IPA (5 ml),
82°C, 24 h.
a
Determined using 1H NMR analysis (average of two runs).
b
19 h.
c
6 h.
intramolecular arene interactions between the phenyl ring
(C45–C50) coordinated to P1 and the phenyl ring (C27–C32)
on P2. The distance between the centroids of the two rings
is 3.6819(1) Å, their average interplane distance is 3.4216 Å
and their offset angle α is 12°.
Figure 1. Molecular structure of 3, showing the atom labelling scheme and
dichloromethane solvated within the asymmetric unit. Displacement
ellipsoids are drawn at 30% probability level. Hydrogen atoms have been
removed for clarity.
79.12(1)° for O2–Ru1–N2. The Ru–P1 and Ru–P2 distances are simi-
lar (2.3506(6) and 2.3505(6) Å, respectively) and fall within the
reported range for ruthenium–phosphine complexes.[20–22] The
Ru–N and Ru–O bond distances (Table 1) are meaningfully longer
than those of previously reported structures.[23–26]
Table 3. TH of carbonyl compounds using complexes 2 and 3
The thiazoline ring has been characterized by puckering
analysis.[27] The thiazoline rings display a larger bond distance
range/average of 31.7–31.1% and the closest description of
the thiazoline rings could be as an envelope conformation on
C8 (S1–N1–C7–C8–C9) and C49 (S2–N2–C17–C18–C9), with
puckering parameters of ϕ(2) = 323.07°, Q(2) = 0.2896 Å and
ϕ(2) = 321.53°, Q(2) = 0.2715 Å, respectively. The dihedral angles
between the two thiazole planes (A → S1/N1/C7–C9; A′ → S2/N2/
C17–C19), the two phenyl planes (B → C1–C6; B′ → C11–C16) and
two chelate planes (C → Ru1/O1/N1/C9/C10; C′ → Ru1/O2/N2/
C19/C20) are 40.80(0.10)° (A/A′), 34.35(13)° (A/B), 33.03(14)° (A′/B′),
26.39(8)° (A/C) and 25.20(10)° (A′/C′). Two chelate ring sys-
tems (C and C′) are close to being perpendicular to each other
(dihedral angle 88.30(7)°), while the phenyl rings (B and B′) are
almost parallel to one another (dihedral angle 22.75(18)°). The
C and C′ chelate rings are planar, and the maximum
deviations from their planes are 0.1679(12) and 0.1486(13)
Å, respectively, for atoms N1 and N2. There are π–π
Entry
1
Substrate
PhCOCH3
Complex
Yield (%)a
—
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
2
3
10
>99
>99
>99
97
2
2′-Cl-PhCOCH3
2′-MeO-PhCOCH3
α-Tetralone
3
>99
96
4
93
68
5
Cyclohexanone
2-Acetylnaphthone
Benzophenone
PhCHO
99
58
6
98
93
7
88
78
8
97
70
9
Methyl isobutyl ketone
2-Acetylpyridine
2-Acetylfuran
82
Table 1. Selected bond lengths (Å) and angles (°) for complex 3
90
Lengths
Angles
10
11
12
99
99
Ru1–O1
Ru1–O2
Ru1–N1
Ru1–N2
S1–C7
2.0818(1)
2.0809(1)
2.1733(1)
2.1551(1)
1.7609(1)
1.7898(1)
1.7603(1)
1.7934(1)
P1–Ru1–N1
P1–Ru1–N2
P2–Ru1–N1
P2–Ru1–N2
N1–Ru1–N2
92.55(1)
161.02(1)
160.31(1)
92.03(1)
82.47(1)
98
98
2-Acetylthiophene
99
98
Reaction conditions: 1 mmol substrate, 1 mmol KOtBu, 1 mol% catalyst,
IPA (5 ml), 82°C, 6 h.
S1–C8
S2–C17
S2–C18
a
Determined using 1H NMR analysis (average of two runs).
Appl. Organometal. Chem. 2016, 30, 373–377
Copyright © 2016 John Wiley & Sons, Ltd.
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Catalytic studies
The synthesized ruthenium complexes 2 and 3 were tested in the
TH reaction of carbonyl compounds. Initially, we started our exper-
iments using acetophenone as a substrate (Table 2). From Table 2, it
is evident that complexes 2 and 3 are active catalysts for TH.
Increasing the amount of the base leads to higher yield in a shorter
time (Table 2, entries 1–6). When KOtBu is used as a base instead of
KOH, the yield is improved (Table 2, entries 1 and 3). Also, there are
several reports of the usage of large amounts of base in TH reaction
catalysed by ruthenium complexes.[28]
After the reaction conditions had been optimized, the ruthenium
complexes 2 and 3 were also tested for various substrates in TH
reaction. In the absence of the catalyst, very low yield (10%) is
obtained (Table 3, entry 1). Generally, moderate to good conversions
(58–99%) are obtained. Among the substrates examined, TH of
benzophenone gives yields of 88 and 78% when using 2 and 3,
respectively (Table 3, entry 7). Also, 68 and 70% yields are obtained
from the TH of α-tetralone and benzaldehyde in the presence of
catalyst 3 (Table 3, entries 4 and 8). We also used cyclic or acylic
aliphatic ketones as substrate. The transformation of cyclohexanone
to cyclohexanol proceeds in moderate yield (58%) using catalyst 3
(Table 3, entry 5). With methyl isobutyl ketone, the yields of the
product are 82 and 90% in the presence of catalysts 2 and 3, respec-
tively (Table 3, entry 9). The reduction of heterocyclic ketones such
as acetylpyridine, furan and thiophene was performed and the
products are obtained in good yields (Table 3, entries 10–12). The
catalytic results are comparable to or even higher than those for
reported procedures.[29]
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Conclusions
Two new thiazoline carboxylate ruthenium complexes (2 and 3)
were easily prepared and used as catalysts for the first time. The
crystal structure of complex 3 was solved by X-ray analysis. Their
catalytic activities were evaluated for TH. These catalyst systems,
especially 2, showed good activity for a range of substrates tested,
and high yields were obtained in the TH reaction.
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Acknowledgements
We thank Ege University Research Fund (2014/Fen/064) for financial
support of this work. We also acknowledge Dokuz Eylul University
for the use of the Agilent Xcalibur Eos difractometer (purchased
under University Research Grant no. 2010.KB.FEN.13).
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