Synthesis of ruthenium(II) complexes derived from reduced imine ligands: As catalysts for transfer hydrogenation of ketones

Article abstract of DOI:10.1016/j.ica.2013.03.004

N-[2-(benzylamino)phenyl]benzenesulfonamide derivatives (1-6) were successfully synthesized by the reaction of imine ligands derived from various N-(2-aminophenyl)benzenesulfonamides and NaBH₄. Then, a series of N-coordinate Ru(II) arene complexes 7-12 were prepared from the reaction of [RuCl₂(p-cymene)]₂ with 1-6. The synthesized compounds were characterized by different methods such as NMR, FT-IR, and elemental analysis. 7-12 were used as catalysts for the transfer hydrogenation (TH) of ketones. At the same time, the effect of various bases such as NaOH, KOH, KOBu^t and Et₃N as organic base were investigated in TH of ketones by 2-propanol as the hydrogen source. 7-12 showed good catalytic activity and so the effects of the different groups were also examined.

Full text of DOI:10.1016/j.ica.2013.03.004

Inorganica Chimica Acta 401 (2013) 107–113
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis of ruthenium(II) complexes derived from reduced imine
ligands: As catalysts for transfer hydrogenation of ketones
b
Serkan Dayan a, Nilgün Kayacı a, Nilgun Ozpozan Kalaycioglu a, , Osman Dayan ,
⇑
Esra Çırçır Öztürk c
a Department of Chemistry, Faculty of Science, Erciyes University, 38039 Kayseri, Turkey
b Laboratory of Inorganic Synthesis and Molecular Catalysis, Çanakkale Onsekiz Mart University, 17020 Çanakkale, Turkey
c Karamanoglu Mehmetbey University, Faculty of Engineering, Department of Material Science & Engineering, TR-70200 Karaman, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
N-[2-(benzylamino)phenyl]benzenesulfonamide derivatives (1–6) were successfully synthesized by the
reaction of imine ligands derived from various N-(2-aminophenyl)benzenesulfonamides and NaBH4.
Then, a series of N-coordinate Ru(II) arene complexes 7–12 were prepared from the reaction of [RuCl2
(p-cymene)]2 with 1–6. The synthesized compounds were characterized by different methods such as
NMR, FT-IR, and elemental analysis. 7–12 were used as catalysts for the transfer hydrogenation (TH) of
ketones. At the same time, the effect of various bases such as NaOH, KOH, KOBut and Et3N as organic base
were investigated in TH of ketones by 2-propanol as the hydrogen source. 7–12 showed good catalytic
activity and so the effects of the different groups were also examined.
Received 27 December 2012
Received in revised form 3 March 2013
Accepted 4 March 2013
Available online 21 March 2013
Keywords:
Transfer hydrogenation
Ru(II) complexes
Sulfonamide
Imine
Crown Copyright Ó 2013 Published by Elsevier B.V. All rights reserved.
1. Introduction
pling [70]. Further, the TH of acetophenone was carried out by
ruthenium(II) complexes of reduced Schiff base ligands. The Ru(II)
In general, sulfonamides are obtained from the reaction of sul-
fonyl chloride with primary or secondary amines in alkaline [1].
The sulfonamides and their derivatives have attracted the interest
of many researchers due to their importance in the development of
coordination chemistry, their application in medicinal chemistry,
catalytic fields, etc. [2–18]. For example, metal complexes contain-
ing sulfonamide ligands have been used as catalysts in different or-
ganic reactions [19–26].
The transfer hydrogenation (TH) of ketones catalyzed by Ru(II)
complexes bearing N-donor ligands has been attracting more and
more attention from the catalysis community [27–38] since the
success of Noyori’s catalyst, bearing 1,2-diamine ligands [39]. After
Noyori et al., researchers, many derivatives of Ru(II) complexes
containing N-donor ligands have aimed to identify a good Ru(II)
catalyst for the TH of ketones. Hereof, ligand groups which have
Ru(II) complexes with unique catalytic activity are sulfonamides.
Otherwise, Schiff base and reduced Schiff base compounds are
also receiving more and more attention in the fields of polymeric
complexes, coordination chemistry, magnetic properties, optical
property, thermal decomposition, medicinal chemistry, catalyst
chemistry, etc. [40–69]. In addition, palladium complexes bearing
diamine and diimine were used as catalyst for Suzuki Cross-Cou-
complexes were found as active catalyst [71]. N-heterocyclic car-
bene (NHC) ligands derivatives from reduced Schiff base ligands
have been synthesized. Then, a series of Ru(II) complexes were pre-
pared with the NHC ligands. The complexes were used for the cat-
alytic transfer hydrogenation of aromatic ketones, recently [72].
In this place, a series of neutral Ru(II) arene complexes derived
from reduced imine ligands bearing aromatic sulfonamide were
synthesized and characterized by various spectroscopic tech-
niques. 7–12 were used as catalysts for the TH of p-substituent ace-
tophenone derivative. The synthesis procedure of ligands 1–6 and
complexes 7–12 are simple and does not require an inert atmo-
sphere and it can be carried out in at mild-temperatures.
2. Experimental
2.1. Materials and methods
All reagents and solvents were obtained from commercial sup-
pliers and used without any additional purification. 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 parts
per million as d downfield from tetramethylsilane (d 0.00) as an
internal standard. Coupling constants (J-values) are given in hertz.
NMR multiplicities are abbreviated as follows: br = broad, s =
⇑
Corresponding author. Tel: +90 505 644 11 70; fax: +90 352 437 49 33.
E-mail address: nozpozan@erciyes.edu.tr (N.O. Kalaycioglu).
0020-1693/$ - see front matter Crown Copyright Ó 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2013.03.004

108
S. Dayan et al. / Inorganica Chimica Acta 401 (2013) 107–113
singlet, d = doublet, t = triplet, m = multiplet signal. The C, H, and N
analyses were performed using a Truspec MICRO (LECO) instru-
ment. Infrared spectra were measured with a Perkin-Elmer Spec-
trum 400 FTIR system and recorded using a universal ATR
sampling accessory within the range 550–4000 cmÀ1. 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 Opti-
ma 5MS capillary column (The GC parameters were as follows:
oven: 80 °C (isothermal); Carrier gas: H2 (Split ratio 15:1); Flow
rate: 4 mL/min; injector port temperature: 220 °C; Detector tem-
(Ar. –C), 127.5 (Ar. –C), 126.6 (Ar. –C), 128.5 (Ar. –C), 128.7 (Ar. –C),
128.9 (Ar. –C), 129.3 (Ar. –C), 130.7 (Ar. –C), 133.0 (Ar. –C), 138.9
(Ar. –C), 145.6 (Ar. –C). IR (cmÀ1): 3434 (–NH–CH2–), 3242 (–NH),
3002, 2909, 2837, 1603, 1583, 1510, 1467, 1445, 1401, 1365
(–SO2), 1323, 1286, 1245, 1207, 1178, 1150 (–SO2), 1092, 1071,
1047, 1029, 992, 989, 913, 832, 807, 753, 740, 730, 711, 686, 632,
595, 558, 535, 462. Anal. Calc. for: C: 65.20, H: 5.47, N: 7.60, O:
13.03, S: 8.70. Found: C: 65.12, H: 5.60, N:7.52, S:8.63%.
(3)-N-[2-(benzylamino)-4-methyl-phenyl]benzenesulfonamide
Color: light pink. Yield: 80%. Mp: 162–163 °C. 1H NMR (CDCl3, d
ppm): 2.35 (s, 3H, –CH3), 4.25 (s, 2H, –CH2–), 6.54–7.80 (15H, –NH–
, H1–4, –H,a–c, and –Hx–y). 13C NMR (CDCl3, ppm): 21.1 (–CH3), 48.22
(–CH2–), 118.0 (Ar. –C), 127.3 (Ar. –C), 127.6 (Ar. –C), 128.5 (Ar. –C),
129.0 (Ar. –C), 129.2 (Ar. –C), 129.3 (Ar. –C), 129.8 (Ar. –C), 130.0
(Ar. –C), 131.9 (Ar. –C), 132.7 (Ar. –C), 133.1 (Ar. –C). IR (cmÀ1):
3441 (–NH–CH2–), 3205 (–NH), 3073, 3045, 3017, 2932, 2916,
2856, 2783, 1600, 1581, 1514, 1482, 1467, 1448, 1436, 1406,
1362 (–SO2), 1326, 1317, 1300, 1282, 1252, 1205, 1179, 1162
(–SO2), 1146, 1128, 1113, 1091, 1072, 1048, 1020, 999, 992, 940,
920, 833, 797, 779, 758, 747, 730, 711, 665, 668, 647, 639, 596,
561, 533, 517, 506, 474. Anal. Calc. for: C: 68.16, H: 5.72, N: 7.95,
O: 9.08, S: 9.10. Found: C: 68.22, H: 5.62, N: 7.99, S: 9.02%.
(4)-N-[2-(benzylamino)-2,4-di-methyl-phenyl]benzenesulfonamide
Color: dark orange. Yield: 78%. Mp: 110–111 °C. 1H NMR (CDCl3,
d ppm): 2.32 (s, 3H, –(CH3)p), 2.34 (s, 3H, –(CH3)o), 4.19 (s, 2H, –
perature: 280 °C; Injection volume: 6.0 lL).
2.2. General procedure for the synthesis of 1–6
N-(2-aminophenyl)benzenesulfonamides and the Schiff base
derivatives of those compounds were prepared in accordance with
the published procedure [73a–c]. Solid sodium borohydride
(0.2 mmol) was added slowly to a solution of N-[2-(benzyl-
amino)phenyl]benzenesulfonamide derivatives (0.2 mmol) in
methanol (10 ml). The solution was stirred at ambient temperature
for a period of 12 h. The volatiles were removed under reduced
pressure. The residue was dissolved in DCM (20 ml) and washed
with H2O (3 Â 50 ml) at room temperature. The organic layer
was separated and dried over anhydrous MgSO4, filtered, and con-
centrated to half of its volume under reduced pressure. The solu-
tion was saturated with diethyl ether and left in the refrigerator
for crystallization. Gradually, a microcrystalline product separated,
which was filtered off, and dried in vacuo (Fig. 1).
CH2–), 4.75 and 6.08 (br. 2H, –NH–), 6.46–7.78 (12H, H1–4, –H,a–c
,
and –Hx–y). 13C NMR (CDCl3, ppm): 18.9 (–(CH3)p), 21.0 (–(CH3)o),
45.7 (–CH2–), 112.0 (Ar. –C), 116.6 (Ar. –C), 120.1 (Ar. –C), 126.8
(Ar. –C), 127.6 (Ar. –C), 128.0 (Ar. –C), 128.7 (Ar. –C), 129.0 (Ar. –
C), 129.5 (Ar. –C), 131.3 (Ar. –C), 133.1 (Ar. –C), 133.4 (Ar. –C),
136.0 (Ar. –C), 136.9 (Ar. –C), 139.0 (Ar. –C), 145.9 (Ar. –C). IR
(cmÀ1): 3431 (–NH–CH2–), 3273 (–NH), 3064, 3001, 2972, 2919,
2866, 1606, 1584, 1520, 1506, 1470, 1448, 1395, 1361 (–SO2),
1326, 1285, 1272, 1248, 1231, 1207, 1179, 1157 (–SO2), 1093,
1070, 1048, 1027, 1000, 980, 932, 925, 906, 873, 852, 827, 813,
784, 757, 739, 729, 712, 686, 638, 597, 565, 553, 536, 489, 462.
Anal. Calc. for: C: 68.82, H: 6.05, N: 7.64, O: 8.73, S: 8.75. Found:
C: 68.90, H: 6.12, N: 7.60, S: 8.66%.
2.2.1. Data for the 1–6
(1)-N-[2-(benzylamino)-phenyl]benzenesulfonamide
Color: light pink. Yield: 92%. Mp: 132–133 °C. 1H NMR (CDCl3, d
ppm): 4.30 (s, 2H, –CH2–), 6.36 (br. –NH–), 6.47–7.35 (9H, –H1–4,
–
Hx–z), 7.46 (t, 2H, J = 8 Hz, –Hb), 7.59 (t, 2H, J = 8 Hz, –Hc), 7.78 (d,
2H, J = 8 Hz, –Ha). 13C NMR (CDCl3, ppm): 48.1 (–CH2–), 112.8 (Ar.
–C), 117.3 (Ar. –C), 120.6 (Ar. –C), 127.3 (Ar. –C), 127.4 (Ar. –C),
127.6 (Ar. –C), 128.6 (Ar. –C), 128.7 (Ar. –C), 129.0 (Ar. –C), 129.4
(Ar. –C), 133.1 (Ar. –C), 138.5 (Ar. –C), 139.0 (Ar. –C), 145.2 (Ar. –
C). IR (cmÀ1): 3426 (–NH–CH2–), 3255 (–NH), 3055, 3027, 2988,
2969, 2902, 1602, 1585, 1515, 1494, 1469, 1453, 1447, 1436,
1394, 1366 (–SO2), 1322, 1298, 1280, 1262, 1208, 1178, 1151
(SO2), 1122, 1088, 1060, 1049, 1026, 996, 974, 941, 909, 880,
858, 834, 804, 779, 750, 736, 727, 712, 697, 685, 665, 635, 590,
564, 539, 500, 485, 458. Anal. Calc. for: C: 67.43, H: 5.36, N: 8.28,
O: 9.46, S: 9.47. Found: C: 67.25, H: 5.16, N: 8.35, S: 9.60%.
(2)-N-[2-(benzylamino)-4-methoxy-phenyl]benzenesulfonamide
Color: light pink. Yield: 84%. Mp: 119–120 °C. 1H NMR (CDCl3, d
ppm): 3.83 (s, 3H, –OCH3), 4.24 (s, 2H, –CH2–) 6.33–7.80 (15H, –
NH– H1–4, –H,a–c and –Hx–y). 13C NMR (CDCl3, ppm): 47.26 (–CH2–),
55.2 (–OCH3), 112.3 (Ar. –C), 114.0 (Ar. –C), 116.7 (Ar. –C), 120.2
(5)-N-[2-(benzylamino)-2,4,6-tri-methyl-phenyl]benzenesulfonamide
Color: white. Yield: 86%. Mp: 152–153 °C. 1H NMR (CDCl3, d
ppm): 2.32 (s, 3H, –(CH3)p), 2.33 (s, 6H, –(CH3)o), 4.15 (s, 2H, –
CH2–), 6.03–7.75 (13H, –NH–, H1–4, –H,a–c, and –Hy). 13C NMR
(CDCl3, ppm): 19.4 (–(CH3)o), 21.0 (–(CH3)p), 42.2 (–CH2–), 111.9
(Ar. –C), 116.6 (Ar. –C), 120.3 (Ar. –C), 127.5 (Ar. –C), 128.5 (Ar. –
C), 128.9 (Ar. –C), 129.1 (Ar. –C), 129.4 (Ar. –C), 131.4 (Ar. –C),
133.0 (Ar. –C), 137.3 (Ar. –C), 137.5 (Ar. –C), 139.0 (Ar. –C), 145.9
(Ar. –C). IR (cmÀ1): 3413 (–NH–CH2–), 3307 (–NH), 3073, 2964,
2923, 2872, 1601, 1584, 1509, 1475, 1447, 1377 (–SO2), 1333,
1320, 1310, 1290, 1274, 1250, 1221, 1208, 1181, 1162 (–SO2),
1121, 1089, 1073, 1063, 1048, 1022, 996, 933, 888, 854, 845,
826, 753, 728, 717, 691, 672, 632, 596, 570, 543, 500, 471. Anal.
Calc. for: C: 69.44, H: 6,36, N: 7.36, O: 8.41, S: 8.43. Found: C:
69.54, H: 6,42, N:7.25, S:8.33%.
a
b
O
H
O
O
H
N
1
4
c
N
S
S
2
3
O
NaBH4
N
HC
NH
H2C
x
MeOH, 12 h.
y
z
R
R
1-6
-C H5 :(1) -p-methoxy-Ph :(2) -p-methyl-Ph: (3) -C6H3Me2-2,4: (4) -C6H2Me3-2,4,6: (5) -p -chloro-Ph: (6)
R=
6
Fig. 1. Synthesis of the ligands together with NMR numbering scheme.

S. Dayan et al. / Inorganica Chimica Acta 401 (2013) 107–113
109
(6)-N-[2-(benzylamino)-4-chloro-phenyl]benzenesulfonamide
(8)-{[N-[2-(benzylamino)-4-methoxy-phenyl]benzenesulfonamide]-
Color: light pink. Yield: 85%. Mp: 151–152 °C. 1H NMR (CDCl3,
d ppm): 4.29 (s, 2H, –CH2–), 6.28 (br. –NH–), 6.45–7.31 (9H, –H1–
(p-cymene)-di-chloro-ruthenium(II)}
Color: dark brown. Yield: 78%. Mp: 122–123 °C. 1H NMR (CDCl3,
d ppm): 1.28 (d, 6H, J = 8 Hz, –Hm), 2.16 (s, 3H, –Hk), 2.92 (m, 1H, –
Hl), 3.81 (s, 3H, –OCH3), 3.75 (s, 2H, –CH2–), 5.35 (d, 2H, J = 8 Hz, –
–Hx–z), 7.47 (t, 2H, J = 8 Hz, –Hb), 7.60 (t, 2H, J = 8 Hz, –Hc), 7.78
4,
(d, 2H, J = 8 Hz, –Ha). 13C NMR (CDCl3, ppm): 47.0 (–CH2–), 112.2
(Ar. –C), 116.8 (Ar. –C), 120.2 (Ar. –C), 127.7 (Ar. –C), 128.6 (Ar. –
C), 128.7 (Ar. –C), 128.9 (Ar. –C), 129.0 (Ar. –C), 129.5 (Ar. –C),
132.8 (Ar. –C), 133.2 (Ar. –C), 137.5 (Ar. –C), 138.7 (Ar. –C),
145.7 (Ar. –C). IR (cmÀ1): 3439 (–NH–CH2–), 3209 (–NH), 3066,
3047, 3033, 2964, 2936, 2903, 2854, 1602, 1581, 1516, 1489,
1468, 1448, 1436, 1409, 1360 (–SO2), 1317, 1290, 1281, 1253,
1206, 1180, 1148 (–SO2), 1129, 1090, 1073, 1049, 1026, 1014,
1001, 993, 939, 921, 856, 832, 806, 756, 745, 731, 711, 684,
639, 596, 556, 533, 472, 456. Anal. Calc. for: C: 61.20, H: 4.60,
N: 7.51, O: 8.58, S: 8.60. Found: C: 61.32, H: 4.50, N: 7.60, S:
8.48%.
Ht), 5.48 (d, 2H, J = 8 Hz, –Hq), 6.61–7.99 (15H, –NH– H1–4, –H,a–c
,
and –Hx–y). 13C NMR (CDCl3, ppm): 18.9 (–CH3), 22.2 (–CH(CH3)2),
30.7 (–CH(CH3)2), 55.2 (–OCH3), 65.9 (–CH2–), 80.6 (Ar. –C), 81.3
(Ar. –C), 82.1 (Ar. –C), 96.8 (Ar. –C), 101.3 (Ar. –C), 113.9 (Ar. –C),
114.0 (Ar. –C), 114.1 (Ar. –C), 114.3 (Ar. –C), 127.3 (Ar. –C), 127.4
(Ar. –C), 127.6 (Ar. –C), 128.4 (Ar. –C), 128.6 (Ar. –C), 128.9 (Ar. –
C), 129.1 (Ar. –C), 129.2 (Ar. –C), 129.3 (Ar. –C), 133.2 (Ar. –C). IR
(cmÀ1): 3434 (–NH–CH2–), 3242 (–NH), 3055, 2961, 2906, 2867,
2836, 1608, 1584, 1511, 1488, 1471, 1464, 1445, 1386, 1323
(–SO2), 1305, 1290, 1247, 1155 (–SO2), 1115, 1087, 1058, 1026,
913, 825, 805, 751, 730, 719, 687, 666, 625, 582, 555, 517, 499,
491, 455. Anal. Calc. for: C: 53.25, H: 5.36, Cl: 10.48, N: 4.14, O:
7.09, Ru: 14.94, S: 4.74. Found: C: 53.87, H: 5.30, N: 4.33, S: 4.96%.
(9)-{[N-[2-(benzylamino)-4-methyl-phenyl]benzenesulfonamide]-
(p-cymene)-di-chloro-ruthenium(II)}
2.3. General procedure for the synthesis of 7–12
A solution of 1–6 (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 reaction mixture was stir-
red for 12 h. 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 in
MeOH and black-colored microcrystals were obtained (Fig. 2).
Color: black. yield: 80%. Mp: 166–168 °C. 1H NMR (CDCl3, d ppm):
1.29 (d, 6H, J = 8 Hz, –Hm), 2.16 (s, 3H, –Hk), 2.29 (s, 3H, –CH3), 2.93
(m, 1H, –Hl), 3.50 (s, 2H, –CH2–), 5.36 (d, 2H, J = 8 Hz, –Ht), 5.49 (d,
2H, J = 8 Hz, –Hq), 6.94–8.06 (15H, –NH–, H1–4, –H,a–c, and –Hx,y).
13C NMR (CDCl3, ppm): 18.9 (–CH3), 21.3 (–CH3)p, 22.2 (–CH(CH3)2),
25.4 (–CH(CH3)2), 60.7 (–CH2–), 80.6 (Ar. –C), 81.3 (Ar. –C), 96.8 (Ar. –
C), 101.3 (Ar. –C), 116.9 (Ar. –C), 127.3 (Ar. –C), 127.6 (Ar. –C), 128.5
(Ar. –C), 129.0 (Ar. –C), 129.2 (Ar. –C), 129.3 (Ar. –C), 129.7 (Ar. –C),
129.9 (Ar. –C), 131.0 (Ar. –C), 131.3 (Ar. –C), 133.3 (Ar. –C). IR
(cmÀ1): 3413 (–NH–CH2–), 3306 (–NH), 3056, 2965, 2923, 2873,
1645, 1602, 1515, 1499, 1489, 1472, 1447, 1388, 1378, 1362
(–SO2), 1325, 1310, 1292, 1158 (–SO2), 1087, 1057, 1035, 1005,
914, 878, 805, 754, 730, 689, 669, 626, 583, 560, 498, 482, 458. Anal.
Calc. for: C: 54.54, H: 5.49, Cl: 10.73, N: 4.24, O: 4.84, Ru: 15.30, S:
4.85. Found: C: 54.42, H: 5.66, N: 4.34, S: 4.92%.
2.3.1. Data for the 7–12
(7)-{[N-[2-(benzylamino)-phenyl]benzenesulfonamide]-(p-cymene)-
di-chloro-ruthenium(II)}
Color: dark brown. Yield: 82%. Mp: 132–133 °C. 1H NMR (CDCl3, d
ppm): 1.27 (d, 6H, J = 8 Hz, –Hm), 2.17 (s, 3H, –Hk), 2.92 (m, 1H, –Hl),
3.49 (s, 2H, –CH2–), 5.34 (d, 2H, J = 8 Hz, –Ht), 5.49 (d, 2H, J = 8 Hz, –
Hq), 6.66–8.12 (16H, –NH– H1–4, –H,a–c, and –Hx–z). 13C NMR (CDCl3,
ppm): 19.0 (–CH3), 22.1 (–CH(CH3)2), 30.6 (–CH(CH3)2), 65.7 (–CH2–
), 80.5 (Ar. –C), 81.4 (Ar. –C), 82.0 (Ar. –C), 96.4 (Ar. –C), 101.0 (Ar. –C),
113.2 (Ar. –C), 113.8 (Ar. –C), 114.1 (Ar. –C), 114.3 (Ar. –C), 127.1 (Ar.
–C), 127.4 (Ar. –C), 127.7 (Ar. –C), 128.0 (Ar. –C), 128.4 (Ar. –C), 128.9
(Ar. –C), 129.0 (Ar. –C), 129.1 (Ar. –C), 129.8 (Ar. –C), 134.2 (Ar. –C). IR
(cmÀ1): 3425 (–NH–CH2–), 3215 (–NH), 3056, 2963, 2925, 2903,
2873, 1645, 1599, 1585, 1531, 1528, 1520, 1496, 1489, 1471, 1464,
1447, 1409, 1368, 1379, 1362 (–SO2), 1325, 1310, 1294, 1261,
1260, 1201, 1157 (–SO2), 1114, 1085, 1058, 1033, 1005, 914, 877,
804, 752, 732, 720, 689, 671, 646, 627, 610, 583, 559, 526, 507,
497, 493, 484, 459. Anal. Calc. for: C: 54.03, H: 5.00, Cl: 11.00, N:
4.35, O: 4.96, Ru: 15.68, S: 4.97. Found: C: 54.15, H: 4.94, N: 4.23,
S: 4.86%.
(10)-{[N-[2-(benzylamino)-2,4-di-methyl-phenyl]benzenesulfon-
amide]-(p-cymene)-di-chloro-ruthenium(II)}
Color: black. Yield: 81%. Mp: 151–152 °C. 1H NMR (CDCl3, d ppm):
1.29 (d, 6H, J = 8 Hz, –Hm), 2.16 (s, 3H, –Hk), 2.40 (s, 3H, –(CH3)o), 2.64
(s, 3H, –(CH3)p), 2.91 (m, 1H, –Hl), 3.52 (s, 2H, –CH2–), 5.36 (d, 2H,
J = 8 Hz, –Ht), 5.49 (d, 2H, J = 8 Hz, –Hq), 6.63–7.80 (14H, –NH–, H1–
4, –H,a–c, and –Hx–y). 13C NMR (CDCl3, ppm): 18.9 (–CH3), 19.5
(–(CH3)o), 21.1 (–(CH3)p), 22.2 (–CH(CH3)2), 30.6 (–CH(CH3)2), 47.1
(–CH2–), 80.6 (Ar. –C), 81.4 (Ar. –C), 96.8 (Ar. –C), 101.3 (Ar. –C),
113.5 (Ar. –C), 118.6 (Ar. –C), 121.1 (Ar. –C), 126.8 (Ar. –C), 127.9
(Ar. –C), 128.0 (Ar. –C), 128.7 (Ar. –C), 129.1 (Ar. –C), 129.4 (Ar. –C),
132.6 (Ar. –C), 133.1 (Ar. –C), 133.3 (Ar. –C), 136.0 (Ar. –C), 136.8
(Ar. –C), 137.1 (Ar. –C), 140.6 (Ar. –C). IR (cmÀ1): 3420 (–NH–CH2–),
b
c
a
O
S
O
H
N
S
O
1
4
k
O
[RuCl2 (p-cymene)]2
MeOH, 60oC, 12 h
NH
2
3
2
Cl
Ru
Cl
NH
H2C
2
H
N
q
t
l
R
R
x
m
z
y
1-6
-p-methoxy-Ph: (8) -p-methyl-Ph: (9)
7-12
-p-chloro-Ph: (12)
R= -C6H5 :(7)
-C6H3Me2-2,4: (10) -C6H2Me3-2,4,6: (11)
Fig. 2. Synthesis of the complexes together with NMR numbering scheme.

110
S. Dayan et al. / Inorganica Chimica Acta 401 (2013) 107–113
Table 1
Catalytic activity for transfer hydrogenation of acetophenone catalyzed by Ru(II) complexes with different base.
Entry
Ru(II) complex
Base
Yield (%)c
TONd
TOFe (hÀ1
)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
23
24
25
7
8
9
10
11
12
7
8
9
10
11
12
7
8
9
10
NaOH
58a, 72b
72a, 80b
62a, 75b
69a, 78b
70a, 77b
73a, 82b
<5b
58a, 72b
72a, 80b
62a, 75b
69a, 78b
70a, 77b
73a, 82b
n.c.b
58a, 36b
72a, 40b
62a, 38b
69a, 39b
70a, 39b
73a, 41b
n.c.b
Et3N
<5b
n.c.b
n.c.b
<5b
n.c.b
n.c.b
<5b
n.c.b
n.c.b
<5b
n.c.b
n.c.b
<5b
n.c.b
n.c.b
KOBut
42a, 58b
60a, 72b
54a, 68b
48a, 62b
55a, 70b
60a, 76b
11a, 16b
<3b
42a, 58b
60a, 72b
54a, 68b
48a, 62b
55a, 70b
60a, 76b
11a, 16b
n.c.b
42a, 29b
60a, 36b
54a, 34b
48a, 31b
55a, 35b
60a, 38b
11a, 8b
n.c.b
11
12
Absence of catalyst
KOH (10 mmol)
Absence of base
KOH (1 mmol)
KOH (0.1 mmol)
KOH
12
12
12
12
12
40a
40a
40a
18a
18a
18a
21a,f
21a
21a
KOH
49a,g
49a
49a
Reaction conditions: 1.0 mmol of acetophenone, 10.0 mmol of Base, 0.01 mmol Ru(II) complexes, 2-propanol (20 mL); all reactions were monitored by TLC and GC; tem-
perature 80 °C.
a
60 min.
120 min.
b
c
GC yields, yields are based on phenylethanol.
TON = moles of product/moles of the catalyst.
d
e
TOF = moles of product/(moles of the catalyst) Â (hour), n.c.: not calculated.
f
T = ambient temperature °C.
g
T = 50 °C.
3307 (–NH), 3056, 2968, 2920, 2902, 1644, 1596, 1500, 1472, 1464,
1446, 1406, 1387, 1379, 1361 (–SO2), 1326, 1310, 1291, 1242, 1201,
1157 (–SO2), 1086, 1056, 1037, 1000, 916, 878, 805, 753, 729, 688,
670, 626, 584, 558, 517, 480, 473, 463, 457. Anal. Calc. for: C: 55.19,
H: 5.68, Cl: 10.51, N: 4.15, O: 4.74, Ru: 14.98, S: 4.75. Found: C:
55.25, H: 5.72, N: 4.22, S: 4.63%.
(12)-{[N-[2-(benzylamino)-4-chloro-phenyl]benzenesulfon-
amide]-(p-cymene)-di-chloro-ruthenium(II)}
Color: dark brown. Yield: 85%. Mp: 160–161 °C. 1H NMR (CDCl3, d
ppm): 1.29 (d, 6H, J = 8 Hz, –Hm), 2.16 (s, 3H, –Hk), 2.90 (m, 1H, –Hl),
4.21 (s, 2H, –CH2–), 5.36 (d, 2H, J = 8 Hz, –Ht), 5.49 (d, 2H, J = 8 Hz, –
Hq), 6.62–7.88 (15H, –NH– H1–4, –H,a–c, and –Hx–y). 13C NMR (CDCl3,
ppm): 19.2 (–CH3), 22.3 (–CH(CH3)2), 30.7 (–CH(CH3)2), 66.2 (–CH2–),
80.7 (Ar. –C), 81.6 (Ar. –C), 82.6 (Ar. –C), 96.7 (Ar. –C), 101.4 (Ar. –C),
113.5 (Ar. –C), 114.0 (Ar. –C), 114.4 (Ar. –C), 114.5 (Ar. –C), 127.4 (Ar.
–C), 127.5 (Ar. –C), 127.9 (Ar. –C), 128.0 (Ar. –C), 128.8 (Ar. –C), 129.2
(Ar. –C), 129.4 (Ar. –C), 129.9 (Ar. –C), 130.0 (Ar. –C), 135.1 (Ar. –C). IR
(cmÀ1): 3460 (–NH–CH2–), 3278 (–NH), 3059, 2955, 2920, 2900,
2888, 1628, 1600, 1578, 1520, 1518, 1505, 1490, 1486, 1465, 1462,
1438, 1400, 1372, 1366, 1355 (–SO2), 1313, 1300, 1290, 1269, 1255,
1200, 1166 (–SO2), 1117, 1092, 1052, 1030, 1003, 916, 872, 801, 742,
722, 710, 682, 661, 641, 621, 613, 588, 565, 523, 517, 487, 482, 480,
455. Anal. Calc. for: C: 51.29, H: 4.60, Cl: 15.66, N: 4.13, O: 4.09,
Ru: 14.88, S: 4.72. Found: C: 51.35, H: 4.52, N: 4.23, S: 4.66%.
(11)-{[N-[2-(benzylamino)-2,4,6-tri-methyl-phenyl]benzenesul-
fonamide]-(p-cymene)-di-chloro-ruthenium(II)}
Color: light brown. Yield: 88%. Mp: 182–183 °C. 1H NMR (CDCl3, d
ppm): 1.28 (d, 6H, J = 8 Hz, –Hm), 2.16 (s, 3H, –Hk), 2.26 (s, 6H, –
(CH3)o), 2.29 (s, 3H, –(CH3)p), 2.92 (m, 1H, –Hl), 4.10 (s, 2H, –CH2–),
5.35 (d, 2H, J = 8 Hz, –Ht), 5.48 (d, 2H, J = 8 Hz, –Hq), 6.63–7.80
(13H, –NH–, H1–4, –H,a–c, and –Hy). 13C NMR (CDCl3, ppm): 18.9
(–CH3), 19.6 (–(CH3)o), 21.0 (–(CH3)p), 22.2 (–CH(CH3)2), 30.7
(–CH(CH3)2), 42.4 (–CH2–), 80.5 (Ar. –C), 81.3 (Ar. –C), 96.8 (Ar. –C),
101.2 (Ar. –C), 109.4 (Ar. –C), 111.9 (Ar. –C), 114.2 (Ar. –C), 116.6
(Ar. –C), 120.3 (Ar. –C), 127.3 (Ar. –C), 127.6 (Ar. –C), 128.9 (Ar. –C),
129.2 (Ar. –C), 129.8 (Ar. –C), 131.4 (Ar. –C), 133.0 (Ar. –C), 137.3
(Ar. –C), 137.5 (Ar. –C), 139.0 (Ar. –C), 145.9 (Ar. –C). IR (cmÀ1):
3413 (–NH–CH2–), 3307 (–NH), 3032, 2966, 2921, 2902, 2873,
1601, 1584, 1510, 1473, 1448, 1409, 1378, 1333 (–SO2), 1321,
1310, 1290, 1275, 1250, 1222, 1208, 1181, 1163, 1121 (–SO2),
1090, 1073, 1057, 1049, 1037, 1006, 997, 933, 889, 863, 854, 845,
827, 805, 759, 754, 729, 717, 692, 633, 598, 571, 544, 500, 478,
472. Anal. Calc. for: C: 55.81, H: 5.85, Cl: 10.30, N: 4.07, O: 4.65,
Ru: 14.68, S: 4.66. Found: C: 55.91, H: 5.77, N: 4.01, S: 4.53%.
2.4. General procedure for the transfer hydrogenation reaction
In a typical experiment, 0.01 mmol of [(p-cymene)RuLCl2],
1 mmol of acetophenone and 10 mmol of KOH were refluxed at
80 °C in 2-propanol (20 ml) as a hydrogen source. After the mixture
was cooled to room temperature, one-fourth of the 2-propanol
were removed under reduced pressure (not dried). The residues

S. Dayan et al. / Inorganica Chimica Acta 401 (2013) 107–113
111
were diluted with diethyl ether (5 ml) and filtered from a mini-col-
umn. The purity of the compounds was checked by GC. The yields
obtained were related to the residual unreacted acetophenone. The
reactions were conducted at a (S/C/base) molar ratio of 1:0.01:10.
singlets at d 4.30, 3.83, 4.25, 4.19, 4.15 and 4.29 ppm, respectively.
In (z) position, –p–OCH3 and –p–CH3 protons were observed as
singlets at d 3.83 ppm for (2) and at d 2.35 ppm for (3); –(CH3)o
and –(CH3)p protons were also observed as singlets at d 2.34 and
2.32 ppm for (4) and at d 2.33 and 2.32 ppm for (5), respectively.
In the 13C NMR spectra for the reduced imine ligands (1–6), the –
NH–CH2– carbons were observed at d 48.1, 47.26, 48.22, 45.7,
42.2 and 47.0 ppm, respectively. Similarly, in (z) position, –p–
OCH3 and –p–CH3 carbons appeared at d 55.2 ppm for (2), and at
d 21.1 ppm for (3); –(CH3)o and –(CH3)p carbons were observed
at d 21.0 and 18.9 ppm for (4) and at d 21.0 and 19.4 ppm for (5),
respectively.
3. Results and discussion
The synthesis and reaction routes of the Ru(II) complexes are
presented in Fig. 2. The synthesized compounds were character-
ized by 1H NMR, 13C NMR and IR spectroscopy techniques.
1–6 were obtained by the reaction of N-[2-(benzyl-
amino)phenyl]benzenesulfonamide with solid sodium borohydride
in methyl alcohol. Then, the novel ruthenium complexes (7–12)
were synthesized by the reaction of 1–6 with [RuCl2(p-cymene)]2
in methyl alcohol. Moreover, [(p-cymene)RuLCl2] (7–12) were used
as catalysts for the TH of acetophenone derivatives.
In the 1H NMR spectra of the Ru(II) complexes (7–12) bearing
reduced imine ligands, the 1H NMR signals shifted to lower fields
for the –NH–CH2– protons compared with 1–6 and were observed
at around d 3.49–4.21 ppm in 7–12. In (z) position, –p–OCH3 and –
p–CH3 protons were observed as singlets at d 3.81 ppm for (8) and
at d 2.29 ppm for (9); –(CH3)o and –(CH3)p protons were also
observed as singlets at d 2.40 and 2.64 ppm for (10) and at d 2.26
and 2.29 ppm for (11), respectively. Additionally, –Hk, –Hq, –Ht, –
Hl and –Hm protons relating to p-cymene exhibited, respectively,
at 2.17, 5.49, 5.34, 2.92, 1.27 ppm in 7; at 2.16, 5.49, 5.35, 2.92,
1.28 ppm in 8; at 2.16, 5.49, 5.36, 2.93, 1.29 ppm in 9; at 2.16,
5.49, 5.36, 2.91, 1.29 ppm in 10; at 2.16, 5.48, 5.35, 2.92,
3.1. NMR spectra
In the 1H NMR spectra for N-[2-(benzylamino)-phenyl]benzene-
sulfonamide ligands (1–6), the –Ha, –Hb and –Hc protons were
observed, respectively, as doublets, triplets and triplets in a 2:2:1
ratio at around d 7.46–7.80 ppm. In the 1H NMR spectra for the re-
duced imine ligands (1–6), –NH–CH2– proton peaks appeared as
Table 2
Catalytic activity for transfer hydrogenation of ketones catalyzed by Ru(II) complexes.
Entry
Ru(II) complex
Substrate
Yield (%)d
TONe
TOFf (hÀ1
)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
23
24
25
26
27
7
8
64a, 90b
69a, 90b
64a, 90b
69a, 90b
256a, 180b
276a, 180b
9
10
11
12
7
8
9
10
11
12
7
74a, 92b
58a, 90b
62a, 87b
78a, 98b
81c
74a, 92b
58a, 90b
62a, 87b
78a, 98b
81c
296a, 184b
232a, 180b
248a, 174b
312a, 196b
81c
80c
80c
80c
83c
83c
83c
78c
78c
78c
84c
84c
84c
88c (33b)
100b
88c(33b)
100b
88c (66b)
200b
8
9
100b
100b
200b
100b
100b
200b
10
11
12
12
12
7
8
9
10
11
12
100b
100b
200b
100b
100b
200b
100b (56a)
46b,g
100b (56a)
200b (224a)
460b,g
840b,h
85c
b,g
230
42b,h
85c
210
b,h
85c
87c
87c
87c
91c
91c
91c
89c
89c
89c
90c
90c
90c
94c (38b)
94c (38b)
94c (76b)
Reaction conditions: 1.0 mmol of substrate, 10.0 mmol of KOH, 0.01 mmol Ru(II) complexes, 2-propanol (20 mL); all reactions were monitored by TLC and GC; temperature
80 °C.
a
15 min.
30 min.
60 min.
b
c
d
GC yields, yields are based on phenylethanol.
TON = moles of product/moles of the catalyst.
e
f
TOF = moles of product/(moles of the catalyst) Â (hour).
g
S/C = 500/1.
h
S/C = 1000/1.

112
S. Dayan et al. / Inorganica Chimica Acta 401 (2013) 107–113
1.28 ppm in 11; at 2.16, 5.49, 5.36, 2.90, 1.29 ppm in 12. In the 13
C
phenone derivatives by using 2-propanol in the presence of base.
The procedure is simple and efficient towards various aryl ketones.
Although all of the complexes are active catalysts for the TH of ke-
tones, conversion was not screened with an organic base such as
Et3N. Ru(II) arene complexes was observed more efficient catalysts
for electron-withdrawing substituent –Cl on the para position of
aryl ring of the ketones. Furthermore, the presence of electron-
withdrawing group on the sulfonamide-ring has a beneficial effect.
Consequently, complex 12 was observed the most active complex
(turnover frequency value: 840 hÀ1 molar ratio S/C: 1000/1). When
examined to TH of Ru(II) arene complexes in the literature, it is
seen that catalysts used in this study have been an passable effi-
ciency in the TH [74–79].
NMR spectra for Ru(II) complexes (7–12), the –NH–CH2– carbons
were observed at d 65.7, 65.9, 60.7, 47.1, 42.4 and 66.2 ppm,
respectively. Similarly, in (z) position, –p–OCH3 and –p–CH3 car-
bons appeared at d 55.2 ppm for (8), and at d 21.3 ppm for (9); –
(CH3)o and –(CH3)p carbons were observed at
d 19.5 and
21.1 ppm for (10) and at d 19.6 and 21.0 ppm for (11), respectively.
The representative NMR spectrums are attached in Fig. S1 as sup-
plementary material.
3.2. Catalytic studies
Catalytic studies with 7–12 were performed for the TH of ace-
tophenone to give phenylethanol in the presence of base by 2-
propanol as a hydrogen source (Table 1). The reaction conditions
for this important process are economic, relatively mild and envi-
ronmentally friendly. The volatile acetone product can also be
easily removed to shift an unfavorable equilibrium. As the start-
ing point, the performances of the catalysts in the transfer hydro-
Acknowledgment
We acknowledge the financial support granted by Erciyes Uni-
versity (ERUBAP), (FBY-11-3783, ID: 3783).
Appendix A. Supplementary material
genation were screened by using acetophenone as
substrate.
a model
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ica.2013.03.004.
In the transfer hydrogenation reaction, the base facilitates the
formation of ruthenium alkoxide by abstracting proton from the
alcohol and subsequently 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 transfer hydrogenation of
ketones. Acetophenone was kept as a test substrate and allowed
it to react in isopropanol with catalytic quantities of complexes
7–12 in the presence of different bases like KOH, NaOH, Et3N
and KOBut. It has been observed that NaOH and KOH have good
conversion when compared to Et3N and KOBut in TH reactions.
The stronger the base the higher the general conversion rankings,
KOH > NaOH > KOBut > Et3N. As in previous studies the best re-
sults were obtained with KOH [37,72]. Hence, it is decided that
base KOH is the best compromise for optimum reaction rate in
isopropanol and reaches 98% conversion for acetophenone within
30 min (Table 1). In the absence of a base no TH of the ketones
was observed. Further, the effect of KOH was investigated in dif-
ferent concentration (10, 1, 0.1 mmol) (Table 1). Moreover, in the
absence of catalyst TH of acetophenone with 10 mmol KOH was
observed as only 16% conversion at 2 h.
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