Novel N-coordinate half-sandwich ruthenium(II) arene complexes bearing sulfonamide fragments: Catalytic activities in the TH of acetophenone derivatives

Article abstract of DOI:10.1016/j.molstruc.2015.06.082

Abstract The novel cationic N-coordinate ruthenium(II)/arene complexes (6-10) were prepared from the starting complex [RuCl₂(p-cymene)]₂ dimer. The structures of the [(p-cymene)RuLCl]Cl (L = N-arenesulfonyl-4,5-dimethyl-o-phenylenedi

Full text of DOI:10.1016/j.molstruc.2015.06.082

Journal of Molecular Structure 1099 (2015) 446e452
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Novel N-coordinate half-sandwich ruthenium(II) arene complexes
bearing sulfonamide fragments: Catalytic activities in the TH of
acetophenone derivatives
Nilgün Kayaci, Serkan Dayan, Nilgun Kalaycioglu Ozpozan*
Department of Chemistry, Faculty of Science, Erciyes University, 38039 Kayseri, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
The novel cationic N-coordinate ruthenium(II)/arene complexes (6e10) were prepared from the starting
complex [RuCl2(p-cymene)]2 dimer. The structures of the [(p-cymene)RuLCl]Cl (L ¼ N-arenesulfonyl-4,5-
dimethyl-o-phenylenediamines) complexes were elucidated by FT-IR, 1H-NMR, 13C-NMR, ionic conduc-
tivity techniques, and elemental analysis methods. The 6e10 complexes were applied as catalyst in the
transfer hydrogenation (TH) of ketones. The catalytic tests showed that all the complexes are moderate
catalysis precursors. Especially, {[N-benzenesulfonyl-4,5-dimethyl-o-phenylenediamine]-(p-cymene)-di-
chloro-ruthenium(II)} (8) and {[N-4-chlorobenzenesulfonyl-4,5-dimethyl-o-phenylenediamine]-(p-
cymene)-di-chloro-ruthenium(II)} (9) compounds were found to be a good catalysts in comparison to the
Received 26 February 2015
Received in revised form
27 June 2015
Accepted 29 June 2015
Available online 6 July 2015
Keywords:
Transfer hydrogenation
Sulfonamide
Ruthenium
others giving the corresponding alcohols in a good turnover frequency value of 1534 and 1731 hꢀ1
respectively.
,
© 2015 Published by Elsevier B.V.
N-coordinate
Synthesis
Characterization
1. Introduction
Moreover, the syntheses of optically active
b-hydroxysulfonamides
have been reported with asymmetric TH of the corresponding
b
-
The ligands bearing sulfonamide moiety are widely used as a
precursor complex in coordination chemistry [1,2]. In addition, the
complexes of bioactive sulfonamide-based ligands have also been
reported [3]. Moreover, the Pd(II) complexes of NHCeN donor
hybrid ligands bearing the sulfonamide group were reported [4].
Furthermore, the properties of ligands and complexes containing
sulfonamide have been investigated in the field of luminescence,
molecular modelling, and in antimicrobial and analytical applica-
tions [5e8]. In addition to the different complexes bearing sul-
fonamides having various catalytic effects, they can also be used as
homogeneous or heterogeneous catalysts in various organic re-
actions, for example, in the oxidation of benzyl alcohol, olefin
metathesis, chiral and achiral transfer hydrogenation, Henry reac-
tion etc. [9e16].
ketosulfonamides using the RueTsDPENeHCOOHeEt3N catalytic
system [19]. In addition, when the Ru(II) complexes of TsDPEN were
used in TH, catalytic activity was found to increasingly depend on
the importance of the NeH bond [20].
Herein, a series of cationic N-coordinate Ru(II) arene complexes
bearing sulfonamide moiety were prepared with an easy and
general method. All the compounds (1e10) were characterized by
using NMR, FT-IR, elemental analysis and ionic conductivity tech-
niques. A cationic Ru(II) arene complexes of 4,5-dimethyl-o-phe-
nylenediamine derivatives bearing sulfonamide fragment is used as
catalyst in the TH of ketones for the first time.
The sulfonamide group can be easily used in the deprotonation
of amide NH [21] or vice versa [22]. All the measurements indicated
that the proposed structure of all the complexes was observed as a
In recent times, the ruthenium(II) or rhodium(III) complexes of
C2-symmetric bis(sulfonamide)-cyclohexane-1,2-diamine-RhCp*
and chiral substituted aromatic monosulfonamide were synthe-
sized and used as catalysts for ATH in isopropanol or water [17,18].
* Corresponding author.
E-mail address: nozpozan@erciyes.edu.tr (N. Kalaycioglu Ozpozan).
http://dx.doi.org/10.1016/j.molstruc.2015.06.082
0022-2860/© 2015 Published by Elsevier B.V.

N. Kayaci et al. / Journal of Molecular Structure 1099 (2015) 446e452
447
type bond. The synthesized Ru(II) complexes were tested as cata-
2.4. Ionic conductivity
lysts in the TH of acetophenones.
Conductance measurements were made at ambient tempera-
ture on 1.00 ꢁ 10ꢀ3 M samples in methyl alcohol. A solution of KCl
(1.00 ꢁ 10ꢀ3 M) was used as the standard. The results of molar
2. Results and discussion
conductance were determined as 92.5
mS for KCl, 84.8
mS for 6,
2.1. Syntheses of all compounds
85.1
m
S for 7, 87.9
mS for 8, 88.2
m
S for 9, and 85.4 S for 10. The
m
results are consistent with the proposed structure of complexes. At
the same time, [Ru(RI-NHSO2-R)] type compounds are also avail-
able in the literature [23].
The synthesis and reaction routes to the ligands and to their
corresponding Ru(II) complexes are presented in Figs. 1 and 2. Li-
gands 1e5 were formed by the reaction of 4,5-dimethyl-o-phe-
nylenediamine with arylsulfonyl chlorides in the presence of
triethylamine in THF (Fig. 1). New cationic ruthenium complexes
6e10 were also obtained by the reaction of 1e5 with [RuCl2(p-
cymene)]2 in methyl alcohol (Fig. 2). All ligands and their com-
plexes were characterized by 1H-NMR, 13C-NMR, FT-IR, elemental
analysis and molar conductance methods.
2.5. Catalysis studies
In recent times, the TH of ketones to alcohols has been exten-
sively investigated [16,23e30]. At the same time, studies are
continuously being aimed at obtaining better catalysts. In the
present work, we successfully synthesized a series of novel ruth-
enium(II) arene complexes bearing sulfonamide fragments (6e10).
The complexes were used as catalysts for the TH of acetophenone
derivatives. The reaction conditions for this important process are
economic, relatively mild and environmentally friendly. The vola-
tile acetone product can also be easily removed to shift an unfav-
ourable equilibrium. As the starting point, the performances of the
catalysts in the TH were screened by using acetophenone as a
model substrate.
2.2. NMR spectra
In the 1H-NMR spectra for 1e5, the -Ha, -Hb protons were
observed as doublets in a 2:2 ratio at around
-H1 and -H2 protons were observed as singlets in a 1:1 ratio at
around 6.15e6.56 ppm. The -Hp and -Ht protons belonging to the
methyls were observed as singlets in a 1:1 ratio at around
1.90e2.12 ppm. In (c) position, the peaks belonging to the -p-CH3,
d 6.91e7.78 ppm. The
d
In the TH reaction, the base facilitates the formation of ruthe-
nium alkoxide by abstracting proton from the alcohol and subse-
d
o-CH3, -p-OCH3 and eC(CH3)3 protons and carbons are shown in
Figures S1-5.
quently alkoxide undergoes
b-elimination to give ruthenium
hydride, which is an active species in this reaction. Since the base
facilitates the formation of ruthenium alkoxide by abstracting the
proton from isopropanol, different bases were used as promoters in
the TH of ketones. Acetophenone was kept as a test substrate and
allowed it to react in isopropanol with catalytic quantities of
complexes 9 (model complex) in the presence of different bases like
KOH, NaOH, KOtBu and K2CO3. NaOH and KOH are known to yield
better conversions than K2CO3 and KOtBu in TH reactions [16,23].
The stronger the base, the higher the general conversion rankings:
KOH > NaOH > KOtBu > K2CO3 (Table 1). In the absence of base, no
TH was observed. Therefore, KOH was selected as the base in all
subsequent studies. Additionally, in the absence of catalyst, the
conversion of TH for acetophenone was founded 16% for 120 min
with excess KOH. In addition, the [RuCl2(p-cymene)]2 complex
were tested as catalyst and the conversion were observed as 45%
under this reaction condition.
N-coordinated complexes were used as nucleophiles to cleave
the [RuCl2(p-cymene)]2 dimer and the resultant N-coordinated
ruthenium complexes (6e10) occurred in high yields. All the
complexes (6e10) were isolated as dark green or black as stable in
the solid state. In the 1H-NMR spectra for 6e10, the protons relating
to p-cymene group were observed at around 1.18e1.28 ppm as
doublet, 2.08e2.18 ppm as singlet, 2.91e2.92 ppm as multiplet,
5.34e5.77 ppm as doublet, 5.47e5.81 ppm as doublet, respectively.
In the 13C-NMR spectra for the Ru(II) complexes (6e10), the peaks
in (c) position belonging to the -p-CH3, o-CH3, -p-OCH3 and
eC(CH3)3 protons and carbons were obtained at 25.6, 26.7, 55.7,
31.1, 31.0 ppm, respectively. The peaks showed a general shift to-
wards lower fields as compared to their respective ligands. The
NMR spectra of all compounds are attached in Figures S1-5 as
supplementary materials.
With these optimized condition, the catalytic experiments re-
2.3. Infrared spectra
sults are shown in Tables 2 and 3. The conversion of 4-
chloroacetophenone is the fastest, giving complete conversion to
the corresponding alcohol at 120 min under the selected operating
conditions (Table 2). It was observed that the activation period was
short for catalyst 9 with an S/C ¼ 500/1 ratio; a 46% conversion rate
was achieved in only 10 min with 4-chloroacetophenone
(TOF ¼ 1390 hꢀ1). Under the same reaction conditions, catalyst 6,
7, 8, 10 had TOF values of 1340, 1210, 1307, 1222 hꢀ1 at 10 min with
In the IR spectra for 1e10, the NeH stretching frequency peaks
belonging to the sulfonamide groups appeared at 3339, 3334, 3335,
3383, 3342 cm-1 for 1e5, at 3151, 3200, 3212, 3218, 3205 cm-1 for
6e10 and NH2 stretching frequency peaks were observed at 3419,
3417, 3414, 3470, 3425 cm-1 for 1e5, at 3243, 3253, 3280, 3296,
3278 cm-1 for 6e10 in the spectra.
Fig. 1. Synthesis of the N-arenesulfonyl-4,5-dimethyl-o-phenylenediamines (1e5).

448
N. Kayaci et al. / Journal of Molecular Structure 1099 (2015) 446e452
Fig. 2. Synthesis of the [(p-cymene)RuLCl]Cl complexes (6e10).
Table 1
Effect of various bases in the TH of acetophenone catalyzed by 9 (0.2 mol-%) in 2-propanol at 82 ꢂC.
Entry
Catalyst
Base
(mmol)
Yield (%)h
TOFj (hꢀ1
)
1
2
3
4
5
6
7
8
9
9
9
9
9
9
NaOH
KOH
(1)
(1)
(1)
(1)
14a
21a
9a
30b
41b
16b
12b
7b
51c
59c
27c
19c
11c
60d
67d
36d
29d
14d
68e
75e
41e
36e
17e
72f
77f
47f
41f
21f
75g
82g
52g
45g
23g
420a
630a
270a
210a
120a
n.c.g
420a
11d
KOBut
K2CO3
KOH
7a
(0.1)
4a
absence of base
KOH
KOH
<5g
14a
11d, 16g
[RuCl2(p-simen)]2
absence of catalyst
(1)
(10)
16b
21c
27d
35e
40f
45g
Reaction conditions: 5.0 mmol of acetophenone, 1 mmol of base, 0.01 mmol Ru(II) complexes, 2-propanol (6 mL); all reactions were monitored by TLC and GC; temperature
80 ꢂC.
a
10 min.
20 min.
40 min.
60 min.
80 min.
100 min.
120 min.
b
c
d
e
f
g
h
GC yields, yields are based on phenyl ethanol, 1TON ¼ moles of product/moles of the catalyst.
j
TOF ¼ moles of product/(moles of the catalyst)x(hour), n. c.: not calculated.
4-chloroacetophenone, respectively.
suppliers and used without any additional purification. The NMR
spectra were recorded at 297 K on a Bruker 400 NMR spectrometer
at 400 MHz (1H) and 100.56 MHz (13C). The NMR studies were
carried out in high-quality 5 mm NMR tubes. Signals are quoted in
Furthermore, the catalytic efficiency of the best catalyst 9 was
also tested in the TH of 4-bromoacetophenone, 4-
floroacetophenone, 2,4,6-trimethylacetophenone (as steric ke-
tones) and cyclohexanone (as aliphatic ketones). In the presence of
parts per million as
d downfield from tetramethylsilane (d 0.00) as
4-bromoacetophenone,
4-floroacetophenone,
2,4,6-
an internal standard. Coupling constants (J-values) are given in
hertz. NMR multiplicities are abbreviated as follows: br ¼ broad,
s ¼ singlet, d ¼ doublet, t ¼ triplet, m ¼ multiplet signal. The C, H,
and N analyses were performed using a Truspec MICRO (LECO)
instrument. Infrared spectra were measured with a PerkineElmer
Spectrum 400 FTIR system and recorded using a universal ATR
sampling accessory within the range 550e4000 cm-1. Melting
points were determined in open capillary tubes on a digital Elec-
trothermal 9100 melting point apparatus. GC measurements for
catalytic experiments were performed using a Younglin Acme
6100 GC instrument with a flame ionization detector and an Optima
5MS capillary column (The GC parameters were as follows: Oven:
80 ꢂC (isothermal); Carrier gas: H2 (Split ratio 15:1); Flow rate:
4 mL/min; Injector port temperature: 220 ꢂC; Detector tempera-
trimethylacetophenone and cyclohexanone conversion rates of
100%, 100%, 19% and 76% respectively were achieved in 100 min
with the best catalyst 9 (Table 2).
Within these frameworks, we also investigated the 4-
chloroacetophenone, 4-methylacetophenone and acetophenone
TH at a (S/C/base) molar ratio of 10:0.01:1 (Table 3). The catalytic
experiments showed that the complexes 8 and 9 are highly effi-
cient. The highest measured TOFs were 1534 and 1731 hꢀ1 for
complexes 8 and 9 in the TH of 4-chloroacetophenone at 10 min,
respectively. When the TH of Ru(II) arene complexes was examined
in the literature, it is seen that the catalysts used in this study had a
good efficiency in the TH [25e30].
ture: 280 ꢂC; Injection volume: 6.0
mL). The peak areas were
founded with the internal standard technique using GC.
3. Experimental
3.1. Materials and methods
3.1.1. General procedure for the synthesis of ligands (L), 1-5
All reagents and solvents were obtained from commercial
N-arenesulfonyl-4,5-dimethyl-o-phenylenediamines
were

N. Kayaci et al. / Journal of Molecular Structure 1099 (2015) 446e452
449
Table 2
Catalytic activity as shown by the % conversion vs. time for the TH of acetophenone, 4-methylacetophenone, 4-chloroacetophenone catalyzed by compounds 6e10 in 2-
propanol. Conditions: p-substitued acetophenone/Ru/KOH, 5:0.01:1; T ¼ 82 ꢂC.
Entry
Catalyst
Substrate
Yield (%)h
TOFj (hꢀ1
)
1
2
3
4
5
6
7
8
6
7
8
9
10
6
7
8
9
10
6
7
8
9
10
9
9
9
9
Acetophenone
23a
27a
21a
21a
18a
3a
40b
33b
41b
41b
37b
6b
45c
47c
51c
59c
43c
18c
22c
26c
21c
24c
68c
69c
75c
71c
63c
80c
81c
8c
56d
54d
65d
67d
55d
35d
30d
36d
30d
33d
72d
76d
84d
87d
72d
91d
92d
13d
61d
63e
57e
74e
75e
61e
38e
34e
37e
37e
38e
82e
80e
89e
95e
76e
98e
99e
17e
69e
67f
63f
78f
77f
67f
43f
40f
43f
42f
44f
87f
84f
94f
98f
82f
100f
100f
19f
76f
78g
75g
80g
82g
68g
48g
48g
50g
53g
49g
93g
88g
97g
100g
88g
100g
100g
21g
81g
685a
798a
616a
635a
525a
98a
4-methylacetophenone
4-chloroacetophenone
4a
7b
128a
165a
210a
179a
1340a
1210a
1307a
1390a
1222a
1470a
1560a
n.c.
5a
10b
12b
9b
9
7a
10
11
12
13
14
15
16
17
18
19
6a
45a
40a
43a
46a
41a
49a
52a
<3a
25a
56b
54b
69b
59b
53b
66b
69b
<3b
36b
4-bromoacetophenone
4-floroacetophenone
2,4,6-trimethylacetophenone
Cyclohexanone
50c
750a
Reaction conditions: 5.0 mmol of substrate, 1.0 mmol of KOH, 0.01 mmol Ru(II) complexes, 2-propanol (6 mL); all reactions were monitored by TLC and GC; temperature 80 ꢂC.
a
10 min.
20 min.
40 min.
60 min.
80 min.
100 min.
120 min.
b
c
d
e
f
g
h
GC yields, the yields obtained were related to the residual unreacted acetophenone and formed phenyl ethanol, 1TON ¼ moles of product/moles of the catalyst.
j
TOF ¼ moles of product/(moles of the catalyst)x(hour). n. c. ¼ not calculated.
Table 3
Catalytic activity as shown by the % conversion vs. time for the TH of (a) acetophenone, (b) 4-methylacetophenone, (c) 4-chloroacetophenone catalyzed by compounds 6e10 in
2-propanol. Conditions: p-substitued acetophenone/Ru/KOH, 10:0.01:1; T ¼ 82 ꢂC.
Entry
Catalyst
Substrate
Yield (%)h
TOFj (hꢀ1
)
1
2
3
4
5
6
7
8
6
7
8
9
10
6
7
8
9
10
6
Acetophenone
24a
14a
20a
27a
21a
4a
32b
33b
29b
41b
30b
9b
45c
44c
40c
52c
39c
18c
18c
22c
24c
17c
66c
51c
45c
60c
59c
52d
51d
50d
61d
42d
23d
26d
29d
29d
28d
78d
58d
72d
70d
77d
57e
56e
58e
65e
53e
40e
38e
35e
37e
36e
85e
67e
79e
77e
80e
58f
60f
62f
67f
59f
45f
42f
42f
45f
40f
87f
71f
90f
85f
84f
65g
66g
69g
70g
64g
47g
45g
48g
49g
45g
88g
80g
91g
94g
86g
1422a
834a
1213a
1617a
1233a
238a
4-methylacetophenone
4-chloroacetophenone
4a
8b
245a
4a
9b
218a
9
5a
11b
10b
51b
31b
30b
45b
40b
296a
10
11
12
13
14
15
4a
271a
28a
21a
26a
29a
28a
1657a
1276a
1534a
1731a
1659a
7
8
9
10
Reaction conditions: 10.0 mmol of substrate, 1.0 mmol of KOH, 0.01 mmol Ru(II) complexes, 2-propanol (6 mL); all reactions were monitored by TLC and GC; temperature 80 ꢂC.
a
10 min.
20 min.
40 min.
60 min.
80 min.
100 min.
120 min.
b
c
d
e
f
g
h
GC yields, the yields obtained were related to the residual unreacted acetophenone formed phenyl ethanol, 1TON ¼ moles of product/moles of the catalyst.
j
TOF ¼ moles of product/(moles of the catalyst)x(hour).
prepared in accordance to the published experimental procedure
[16,23,24].
reaction continued for a period of 12 h. A solid filtrate was left as a
by-product. The volatiles were removed under reduced pressure
(Fig. 1). The residue was dissolved in DCM (20 ml) and washed with
H2O (3 ꢁ 50 ml) at room temperature. The organic layer was
separated and dried over anhydrous MgSO4, filtered, and concen-
trated to half of its volume under reduced pressure. An analytically
pure sample can be isolated by recrystallization from chloroform/
A solution of benzenesulfonylchlorides (5 mmol) in THF (10 ml)
was added drop wise to a solution of triethylamine (10 mmol) with
a dropping funnel in THF (5 ml) in a Schlenk tube. After a few mi-
nutes, a THF (5 ml) solution of 4,5-dimethyl-o-phenylenediamine
(5 mmol) was added slowly at ambient temperature, and the

450
N. Kayaci et al. / Journal of Molecular Structure 1099 (2015) 446e452
diethyl ether (12 ml 1:5, v/v).
SO2), 1111, 1086, 1016, 1005, 918, 883, 859, 842, 832, 754, 732, 682,
666, 624, 571 ( -SO2), 555, 537, 521, 495, 476, 467, 457. Anal. Calcd.
D
3.1.1.1. Data for the ligands 1-5
For: [C18H24N2O2S] C: 65.03, H: 7.28, N: 8.43, S: 9.64. Found: C:
64.93, H: 7.39, N: 8.37, S: 9.77.
3.1.1.1.1. For N-4-methoxybenzenesulfonyl-4,5-dimethyl-o-phe-
nylenediamine (1). Color: Light Brown. Yield: 84%. Mp: 144 ꢂC. 1H-
NMR (CDCl3,
d
ppm): 1.96 (s, 3H, -Ht), 2.11 (s, 3H, -Hp), 3.85 (s, 3H,
3.1.2. General procedure for the synthesis of [(p-cymene)RuLCl]Cl,
6-10
-OCH3), 6.33 (s, 1H, -H2), 6.53 (s, 1H, -H1), 6.91 (d, 2H, J ¼ 8 Hz, -Hb),
7.68 (d, 2H, J ¼ 8 Hz, -Ha). 13C-NMR (CDCl3, ppm): 18.6 (-CH3 (p)),
19.5 (-CH3 (t)), 55.6 (-OCH3), 114.0 (-Cb), 118.6 (-C2), 119.1 (-C1), 127.0
(-Ci3), 129.5 (-Ci4), 129.7 (-Ca), 130.9 (-Ci5), 137.3 (-Ci1), 141.7 (-Ci2),
163.0 (-Cc). IR (cmꢀ1): 3419 (-NH2), 3339 (-NH), 3092, 3062, 3029,
2984, 2949, 1619, 1593, 1575, 1512, 1494, 1456, 1442, 1417, 1391,
1374, 1322 (nas-SO2), 1306, 1295, 1248, 1224, 1175, 1153 (ns-SO2),
1106, 1090, 1012, 910, 881, 863, 837, 801, 761, 743, 717, 662, 629, 621,
579, 567, 555 (D-SO2), 508, 500, 491, 483, 464, 458. Anal. Calcd. For:
[C15H18N2O3S] C: 58.80, H: 5.92, N: 15.67, S: 10.47. Found: C: 58.88,
H: 5.99, N: 15.56, S: 10.55.
3.1.1.1.2. For
phenylenediamine (2). Color: Light Brown. Yield: 83%. Mp: 95 ꢂC.
1H-NMR (CDCl3,
ppm): 1.90 (s, 3H, -Ht), 2.09 (s, 3H, -Hp), 2.30 (s,
A solution of 1e5 (0.50 mmol) in methyl alcohol (5 ml) was
added to a solution of [RuCl2(p-cymene)]2 (0.25 mmol) in methyl
alcohol (5 ml) in a Schlenk tube. The mixture was stirred for 12 h
with a magnetic stirrer. After completion of the reaction time, the
volatiles were removed under reduced pressure. The residue was
washed with diethyl ether (20 ml) and dried under vacuum. The
desired products were recrystallized from MeOH to give black or
dark green-colored microcrystals (Fig. 2). The synthesized ruth-
enium(II) arene complexes are highly soluble in polar organic sol-
vents such as chloroform, dichloromethane, DMSO and DMF and
they are almost insoluble in diethyl ether and petroleum ether. The
analytical data (C, H, N and S) are in good agreement with the
compositions proposed for all the complexes.
N-2,4,6-trimethylbenzenesulfonyl-4,5-dimethyl-o-
d
3H, p-CH3), 2.47 (s, 6H, o-CH3), 6.15 (s,1H, -H2), 6.52 (s,1H, -H1), 6.92
(s, 2H, -Hb). 13C-NMR (CDCl3, ppm): 18.5 (-CH3(p)), 19.5 (-CH3 (t)),
21.0 (p-CH3), 23.1 (o-CH3), 118.5 (-C2), 118.7 (-C1), 126.9 (-Ci3), 129.5
(-Ci4), 131.8 (-Cb), 133.7 (-Ci5), 137.4 (-Ci1), 139.5 (-Ca), 142.1 (-Ci2),
142.4 (-Cc). IR (cmꢀ1): 3417 (-NH2), 3334 (-NH), 3020, 2973, 2938,
2860, 1623, 1601, 1563, 1510, 1455, 1399, 1380, 1365, 1308 (nas-SO2),
1267, 1221, 1186, 1146 (ns-SO2), 1087,1057, 1033, 1003, 965, 910, 855,
749, 728, 679, 648, 621, 577, 535, 512 (D-SO2), 470, 457. Anal. Calcd.
For: [C17H22N2O2S] C: 64.12, H: 6.96, N: 8.80, S: 10.07. Found: C:
64.21, H: 7.08, N: 8.84, S: 10.01.
3.1.2.1. For {[N-4-methoxybenzenesulfonyl-4,5-dimethyl-o-phenyl-
enediamine]-(p-cymene)-di-chloro-ruthenium(II)} (6). Color: Black.
Yield: 86%. Mp: 165 ꢂC. 1H-NMR (CDCl3,
d ppm): 1.28 (d, 6H,
J ¼ 8 Hz, -Hm), 2.05 (s, 3H, -Ht), 2.15 (s, 6H, -Hp, -Hk), 2.91 (m, 1H,
-Hl), 3.85 (s, 3H, -OCH3), 5.35 (d, 2H, J ¼ 4 Hz, -Hy), 5.47 (d, 2H,
J ¼ 4 Hz, -Hx), 6.74e8.07 (6H, -H1,2, -Ha,b). 13C-NMR (CDCl3, ppm):
18.9 (-CH3 (p), -CH3 (k)), 19.3 (-CH3 (t)), 22.2 (-CH(CH3)2), 30.7
(-CH(CH3)2), 55.7 (-OCH3), 80.6, 81.3, 96.8, 101.2, 114.1 (-Cb), 116.4
(-C2), 119.1 (-C1), 127.2 (-Ci3), 128.9 (-Ci4), 129.8 (-Ca), 130.8 (-Ci5),
135.9 (-Ci1), 141.4 (-Ci2), 163.1 (-Cc). IR (cmꢀ1): 3243 (-NH2), 3151
(-NH), 3055, 2973, 2945, 2869, 1688, 1649, 1594, 1580, 1497, 1470,
1456, 1415, 1386, 1300 (nas-SO2), 1255, 1180, 1151 (ns-SO2), 1087,
3.1.1.1.3. For
amine (3). Color: Light Pink. Yield: 82%. Mp: 117 ꢂC. 1H-NMR
(CDCl3, ppm): 1.93 (s, 3H, -Ht), 2.10 (s, 3H, -Hp), 6.29 (s, 1H, -H2),
N-benzenesulfonyl-4,5-dimethyl-o-phenylenedi-
d
6.56 (s, 1H, -H1), 7.41e7.78 (m, 5H, -Ha-c). 13C-NMR (CDCl3, ppm):
18.5 (-CH3 (p)), 19.5 (-CH3 (t)), 118.9 (-C2), 126.0 (-C1), 127.5 (-Ca),
127.6 (-Ci3), 128.9 (-Ci4), 129.5 (-Cb), 132.9 (-Cc), 133.0 (-Ci1), 137.5
(-Ci5), 139.2 (-Ci2). IR (cmꢀ1): 3414 (-NH2), 3335 (-NH), 3031, 2980,
2950, 2916, 2864, 1616, 1604, 1584, 1515, 1473, 1447, 1391, 1373,
1325 (nas-SO2), 1309, 1293, 1270, 1223, 1197, 1164, 1155 (ns-SO2),
1123, 1089, 1070, 1033, 1025, 1015, 998, 917, 900, 883, 862, 777, 758,
1058,1022,1005, 901, 877, 834, 802, 780, 716, 667, 628, 608, 558 (D-
SO2). Anal. Calcd. For: C: 49.02, H: 5.27, N: 4.57, S: 5.23. Found: C:
49.11, H: 5.33, N: 4.50, S: 5.21.
3.1.2.2. For {[N-2,4,6-trimethylbenzenesulfonyl-4,5-dimethyl-o-phe-
nylenediamine]-(p-cymene)-di-chloro-ruthenium(II)}
(7). Color:
ppm): 1.18 (d,
Dark Green. Yield: 87%. Mp: 178 ꢂC.1H-NMR (DMSO,
d
720, 690, 623, 612, 590, 574, 559 (
Calcd. For: [C14H16N2O2S] C: 60.85, H: 5.84, N: 10.14, S: 11.60.
Found: C: 60.72, H: 5.92, N: 10.08, S: 11.52.
D
-SO2), 534, 513, 482, 460. Anal.
6H, J ¼ 8 Hz, -Hm), 1.95 (s, 3H, -Ht), 2.08 (s, 6H, -Hp, -Hk), 2.23 (s, 3H,
p-CH3), 2.41 (s, 3H, o-CH3), 2.91 (m, 1H, -Hl), 5.77 (d, 2H, J ¼ 4 Hz,
-Hy), 5.81 (d, 2H, J ¼ 4 Hz, -Hx), 6.46 (s, 1H, -H2), 6.74 (s, 1H, -H1),
6.98 (s, 2H, -Hb). 13C-NMR (DMSO, ppm): 23.1 (-CH3 (p), -CH3 (k)),
23.8 (-CH3 (t)), 25.6 (p-CH3), 26.7 (o-CH3, eCH(CH3)2), 35.2
(-CH(CH3)2), 90.7, 91.6, 105.3, 111.7, 121.6 (-C2), 128.1 (-C1), 130.2
(-Ci3), 135 (-Ci4), 135.9 (-Cb), 136.7 (-Ci5), 136.8 (-Ci1), 137.0 (-Ca),
144.0 (-Ci2), 155.3 (-Cc). IR (cmꢀ1): 3253 (-NH2), 3200 (-NH), 3050,
2965, 2872, 1691, 1646, 1603, 1564, 1514, 1506, 1471, 1455, 1403,
1386, 1323 (nas-SO2), 1263, 1223, 1187, 1150 (ns-SO2), 1087, 1055,
3.1.1.1.4. For N-4-chlorobenzenesulfonyl-4,5-dimethyl-o-phenyl-
enediamine (4). Color: Light Pink. Yield: 83%. Mp: 120 ꢂC. 1H-NMR
(CDCl3,
d ppm): 1.97 (s, 3H, -Ht), 2.12 (s, 3H, -Hp), 6.31 (s, 1H, -H2),
6.56 (s, 1H, -H1), 7.42 (d, 2H, J ¼ 8 Hz, -Hb), 7.69 (d, 2H, J ¼ 8 Hz, -Ha).
13C-NMR (CDCl3, ppm): 18.6 (-CH3 (p)), 19.5 (-CH3 (t)), 118.8 (-C2),
119.0 (-C1), 127.6 (-Ca), 129.0 (-Ci3), 129.1 (-Ci4), 129.3 (-Cb), 137.4
(-Ci1), 137.8 (-Cc), 139.4 (-Ci5), 141.1 (-Ci2). IR (cmꢀ1): 3470 (-NH2),
3383 (-NH), 3093, 3021, 2970, 2921, 2859, 1626, 1575, 1510, 1475,
1456, 1393, 1314 (nas-SO2), 1280, 1218, 1160 (ns-SO2), 1090, 1033,
1032, 1013, 966, 878, 852, 804, 703, 655, 587, 573, 528 (D-SO2), 457.
Anal. Calcd. For: C: 51.92, H: 5.81, N: 4.48, S: 5.13. Found: C: 51.99, H:
5.75, N: 4.43, S: 5.18.
1005, 916, 881, 855, 822, 752, 706, 648, 626, 604, 583 (D-SO2), 539,
481. Anal. Calcd. For: [C14H15N2O2S] C: 54.10, H: 4.86, N: 9.01, S:
10.32. Found: C: 54.02, H: 4.93, N: 9.15, S: 10.27.
3.1.2.3. For {[N-benzenesulfonyl-4,5-dimethyl-o-phenylenediamine]-
3.1.1.1.5. For N-4-tert-butylbenzenesulfonyl-4,5-dimethyl-o-phe-
(p-cymene)-di-chloro-ruthenium(II)} (8). Color: Dark Green. Yield:
nylenediamine (5). Color: Light Pink. Yield: 81%. Mp: 134 ꢂC. 1H-
86%. Mp: 137 ꢂC.1H-NMR (CDCl3,
d
ppm): 1.28 (d, 6H, J ¼ 8 Hz, -Hm),
NMR (CDCl3,
d
ppm): 1.34 (s, 9H, eC(CH3)3), 1.91 (s, 3H, -Ht), 2.11 (s,
2.03 (s, 3H, -Ht), 2.15 (s, 6H, -Hp, -Hk), 2.91 (m, 1H, -Hl), 5.34 (d, 2H,
J ¼ 4 Hz, -Hy), 5.48 (d, 2H, J ¼ 4 Hz, -Hx), 6.69 (s, 1H, -H2), 6.99 (s, 1H,
-H1), 7.35e8.14 (m, 5H, -Ha-c). 13C-NMR (CDCl3, ppm): 18.9 (-CH3 (p),
-CH3 (k)), 19.3 (-CH3 (t)), 22.2 (-CH(CH3)2), 30.7 (-CH(CH3)2), 80.6,
81.3, 96.8, 101.3, 124.4 (-C2), 126.0 (-C1), 126.5 (-Ca), 127.3 (-Ci3),
127.5 (-Ci4), 127.9 (-Cb), 128.6 (-Cc), 128.9 (-Ci1), 131.8 (-Ci5), 133.1
(-Ci2). IR (cmꢀ1): 3280 (-NH2), 3212 (-NH), 3058, 2964, 2925, 2872,
1687, 1646, 1608, 1558, 1512, 1471, 1446, 1387, 1326 (nas-SO2), 1310,
3H, -Hp), 6.19 (s, 1H, -H2), 6.55 (s, 1H, -H1), 7.46 (d, 2H, J ¼ 8 Hz, -Hb),
7.68 (d, 2H, J ¼ 8 Hz, -Ha). 13C-NMR (CDCl3, ppm): 18.5 (-CH3 (p)),
19.5 (-CH3 (t)), 31.1 (-C(CH3)3), 35.2 (-C(CH3)3), 118.7 (-C2), 119.0
(-C1), 125.8 (-Cb), 126.9 (-Ca), 127.5 (-Ci3), 129.5 (-Ci4), 136.0 (-Ci1),
137.4 (-Ci5), 141.7 (-Ci2), 156.8 (-Cc). IR (cmꢀ1): 3425 (-NH2), 3342
(-NH), 3073, 2954, 2907, 2867, 1595, 1514, 1506, 1479, 1463, 1456,
1395, 1363, 1325 (nas-SO2), 1309, 1293, 1267, 1223, 1195, 1161 (ns
-

N. Kayaci et al. / Journal of Molecular Structure 1099 (2015) 446e452
451
Fig. 3. TH of acetophenone derivatives to corresponding alcohols with [RuCl(p-cymene)L]Cl.
1289, 1263, 1158 (ns-SO2), 1087, 1058, 1033, 1018, 904, 876, 846, 804,
756, 723, 689, 667, 611, 580, 544 ( -SO2), 480. Anal. Calcd. For: C:
49.48, H: 5.19, N: 4.81, S: 5.50. Found: C: 49.53, H: 5.25, N: 4.73, S:
5.61.
the substituents of the aromatic ketones. Within these frameworks,
the best result was obtained in the presence of the eCl substituent
at the para position of the sulfonamide aryl group. Additionally, the
electron-withdrawing group (-Cl, -F, -Br) introduced into the para
position of the acetophenone increased the yield, whereas the
electron-donating group (-CH3) at the para position of the aceto-
phenone decreased the yield. Moreover, when 2,4,6-trimethylace-
tophenone was used as a substrate, a constant decrease in the
catalytic yield was observed, which was probably due to steric ef-
fects. Furthermore, the best catalyst 9 was observed as effective
catalyst for TH of aliphatic ketones (cyclohexanone). So that this
type ruthenium(II) complexes were determined as active catalysts
in the TH of aliphatic ketones. The catalytic activity for the TH of
ketones increases in the order 10 < 7 < 6 < 8 < 9.
D
3.1.2.4. For
enediamine]-(p-cymene)-di-chloro-ruthenium(II)} (9). Color: Dark
Green. Yield: 87%. Mp: 171 ꢂC. 1H-NMR (CDCl3,
ppm): 1.28 (d, 6H,
{[N-4-chlorobenzenesulfonyl-4,5-dimethyl-o-phenyl-
d
J ¼ 8 Hz, -Hm), 2.26 (s, 3H, -Ht), 2.18 (s, 6H, -Hp, -Hk), 2.91 (m, 1H,
-Hl), 5.34 (d, 2H, J ¼ 4 Hz, -Hy), 5.48 (d, 2H, J ¼ 4 Hz, -Hx), 6.88e8.09
(7H, -Ha-c, -H1,2). 13C-NMR (CDCl3, ppm): 18.9 (-CH3 (p), -CH3 (k)),
19.4 (-CH3 (t)), 22.1 (-CH(CH3)2), 30.6 (-CH(CH3)2), 80.6, 81.3, 96.8,
101.3, 121.8 (-C2), 124.3 (-C1), 126.6 (-Ca), 128.2 (-Ci3), 128.9 (-Ci4),
129.4 (-Cb), 129.5 (-Ci1), 130.2 (-Cc), 135.3 (-Ci5), 139.6 (-Ci2). IR
(cmꢀ1): 3296 (-NH2), 3218 (-NH), 3057, 3035, 2964, 2924, 2872,
1607, 1585, 1515, 1474, 1455, 1390, 1327 (nas-SO2), 1293, 1280, 1264,
1161 (ns-SO2), 1086, 1058, 1033, 1013, 908, 877, 827, 805, 754, 706,
Acknowledgments
614, 576, 543 (D-SO2), 480. Anal. Calcd. For: C: 46.72, H: 4.74, N:
4.54, S: 5.20. Found: C: 46.85, H: 4.69, N: 4.43, S: 5.29.
We acknowledge the financial support granted by Erciyes Uni-
versity (ERUBAP), (FBY-12-4171, ID: 4171).
3.1.2.5. For {[N-4-tert-butylbenzenesulfonyl-4,5-dimethyl-o-phenyl-
Appendix A. Supplementary data
enediamine]-(p-cymene)-di-chloro-ruthenium(II)}
(10). Color:
ppm): 1.28 (d, 6H,
Black. Yield: 81%. Mp: 186 ꢂC. 1H-NMR (CDCl3,
d
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.molstruc.2015.06.082.
J ¼ 8 Hz, -Hm), 1.34 (s, 9H, eC(CH3)3), 2.16 (s, 6H, -Hp, -Hk), 2.25 (s,
3H, -Ht), 2.92 (m, 1H, -Hl), 5.35 (d, 2H, J ¼ 4 Hz, -Hy), 5.48 (d, 2H,
J ¼ 4 Hz, -Hx), 6.70e8.05 (6H, -Ha,b,1,2). 13C-NMR (CDCl3, ppm): 18.9
(-CH3 (p), -CH3 (k)), 19.3 (-CH3 (t)), 22.1 (-CH(CH3)2), 30.6
(-CH(CH3)2), 31.0 (-C(CH3)3), 31.1 (-C(CH3)3), 80.6, 81.3, 96.8, 101.3,
124.3 (-C2), 125.0 (-C1), 126.2 (-Cb), 126.4 (-Ca), 127.2 (-Ci3), 127.4
(-Ci4), 128.4 (-Ci1), 129.0 (-Ci5), 138.0 (-Ci2), 152.7 (-Cc). IR (cmꢀ1):
3278 (-NH2), 3205 (-NH), 3049, 2962, 2928, 2870, 1596, 1514, 1506,
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