Synthesis and characterization of half-sandwich ruthenium complexes containing aromatic sulfonamides bearing pyridinyl rings: Catalysts for transfer hydrogenation of acetophenone derivatives

Article abstract of DOI:10.1002/ejic.201300266

N-(Quinoline-8-yl-aryl)benzenesulfonamides 1-6 were successfully synthesized by the reaction of 8-aminoquinoline and various benzenesulfonyl chlorides. Then, half-sandwich ruthenium complexes 7-12 were prepared from the reactions of 1-6 with [RuCl₂(p-cymene)]₂. The synthesized compounds were characterized by NMR and FTIR spectroscopy and elemental analysis, and compounds 8 and 9 were further analyzed by X-ray diffraction. The complexes were screened for their efficiency as catalysts in the transfer hydrogenation of acetophenone derivatives to phenylethanols in the presence of KOH with 2-propanol (as hydrogen source) at 82 °C, and they all showed good activity. Complexes 10 and 12 were the most active (turnover frequency values: 703 and 734 h^-1, respectively). A series of new half-sandwich Ru ^II complexes containing sulfonamide ligands were synthesized and characterized by NMR and FTIR spectroscopy and elemental analysis, and two of the complexes were further analyzed by X-ray diffraction. We investigated the catalytic activity of these complexes in the transfer hydrogenation of a few acetophenone derivatives with the use of 2-propanol in the presence of base. Copyright

Full text of DOI:10.1002/ejic.201300266

FULL PAPER
DOI:10.1002/ejic.201300266
Synthesis and Characterization of Half-Sandwich
Ruthenium Complexes Containing Aromatic Sulfonamides
Bearing Pyridinyl Rings: Catalysts for Transfer
Hydrogenation of Acetophenone Derivatives
Serkan Dayan,[a] Nilgun Ozpozan Kalaycioglu,*[a]
Jean-Claude Daran,[b,c] Agnès Labande,[b] and Rinaldo Poli[b,c,d]
Keywords: Transfer hydrogenation / Sulfonamides / Ruthenium / N ligands
N-(Quinoline-8-yl-aryl)benzenesulfonamides 1–6 were suc-
cessfully synthesized by the reaction of 8-aminoquinoline
and various benzenesulfonyl chlorides. Then, half-sandwich
ruthenium complexes 7–12 were prepared from the reactions
of 1–6 with [RuCl2(p-cymene)]2. The synthesized compounds
lyzed by X-ray diffraction. The complexes were screened for
their efficiency as catalysts in the transfer hydrogenation of
acetophenone derivatives to phenylethanols in the presence
of KOH with 2-propanol (as hydrogen source) at 82 °C, and
they all showed good activity. Complexes 10 and 12 were
were characterized by NMR and FTIR spectroscopy and ele- the most active (turnover frequency values: 703 and 734 h–1
,
mental analysis, and compounds 8 and 9 were further ana- respectively).
same time, half-sandwich ruthenium(II) complexes contain-
ing thioamides, 2-(diphenylphosphanyl)aniline, ferrocenyl
tosylamine-phosphane and pyridine-based chelating di-
amine ligands were also studied for the catalytic TH of
ketones.[34–37] Also, remarkable studies have been carried
out in the TH of acetophenone derivatives.[38–52]
Introduction
Sulfonamides are widely used in the field of coordination
chemistry[1–4] and have also been investigated for their lumi-
nescent and antimicrobial properties and for analytical ap-
plications.[5–7] Many sulfonamide derivatives and their com-
plexes have been recently reported.[8a–8d] Furthermore, com-
plexes containing sulfonamide groups have been used to
catalyze various organic reactions, for example, olefin me-
tathesis, asymmetric transfer hydrogenation (TH), the nitro-
aldol (Henry) reaction, and so on.[9–11] Sulfonamides
containing 8-aminoquinoline have rarely been studied by
the scientific community, and mostly only in relation to
their luminescent properties.[12–16] Also, catalysis and the
molecular structural properties of sulfonamides have re-
cently been studied in detail by our research team.[17a–17d]
Ketone TH catalyzed by RuII complexes containing N-
donor ligands has attracted increasing attention[18–32] since
the success of Noyori’s work using 1,2-diamine ligands.[33]
Several diamine ligand modifications have been explored
aimed at developing catalysts with increased activity. At the
Herein, a series of half-sandwich RuII complexes contain-
ing sulfonamide ligands were synthesized and characterized
by various spectroscopic techniques. The synthesized com-
plexes were used as catalysts for the TH of acetophenone
derivatives.
Results and Discussion
Syntheses
The synthesis and reaction routes to the ligands and to
their corresponding RuII complexes are presented in Fig-
[a] Department of Chemistry, Faculty of Science, Erciyes
University,
38039 Kayseri, Turkey
Fax: +90-352-437-4933
E-mail: nozpozan@erciyes.edu.tr
Homepage: http://aves.erciyes.edu.tr/SorguKimlikBilgileri.
aspx?Sorgu=789
[b] CNRS, LCC,
31077 Toulouse, France
[c] Univ. Toulouse, UPS, INPT,
31077 Toulouse, France
Figure 1. Synthesis of the ligands together with their NMR num-
bering scheme.
[d] Inst. Univ. France,
75005 Paris, France
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Figure 2. Synthesis of the complexes together with their NMR numbering scheme.
ures 1 and 2. Ligands 1–6 were obtained by the reaction of
8-aminoquinoline with R-arylsulfonyl chlorides in the pres-
ence of triethylamine in THF (Figure 1). Then, ruthenium
complexes 7–12 were synthesized by the reactions of 1–6
with [RuCl2(p-cymene)]2 in methyl alcohol (Figure 2). All
compounds were characterized by 1H NMR, 13C NMR,
and IR spectroscopy. In addition, the solid-state structures
of complexes 8 and 9 were confirmed by X-ray crystallogra-
phy.
Crystal Structures
Molecular views of compounds 8 and 9 are shown in
Figure 3. In each complex, the Ru atom has a pseudotetra-
hedral geometry; the η6-π-bonded arene rings occupy one
vertex of the tetrahedron, and the three other vertices are
occupied by the two N atoms of the pyridinyl ligands and
the Cl atoms. Selected bond lengths and angles are shown
in Table 1. Such geometry is common for all η6-ruthenium
arene complexes.[56–58]
NMR Spectra
1
In the H NMR spectra of ligands 1–6, the Ha, Hb, and
Hc protons were observed as a doublet and two triplets,
respectively, in a 2:2:1 ratio at around δ = 7.79–7.88 ppm in
N-quinoline-8-yl-benzenesulfonamide. Similarly, in other
N-quinoline-8-yl-arylsulfonamide ligands, the Ha and Hb
protons were observed as doublets in a 2:2 ratio at around
δ = 6.99–8.80 ppm. The NH protons were found at around
δ = 9.31–11.66 ppm.
1
In the H NMR spectra of 7–12, the sulfonamide NH
proton is no longer present, whereas new resonances be-
longing to the p-cymene group (Hk, Hx, Hy, Hl, and Hm)
appear (Table 2).
Figure 3. Molecular views of compounds 8 and 9 with the atom
labeling scheme; ellipsoids are drawn at the 50% probability level.
H atoms are represented as small spheres of arbitrary radii.
Infrared Spectra
The sulfonamide N–H stretching band for ligands 1–6
appears at 3260–3192 cm–1 (Table 3). This band disappears observed at higher frequencies than their respective ligands.
on going to ruthenium complexes 7–12. The frequencies of However, the symmetric stretches also underwent a general
the SO2 stretching and bending peaks are shown in Table 3. shift toward lower frequencies as compared to their respec-
For 7–12, the bending and asymmetric stretching bands are tive ligands.
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Table 1. Comparison of selected bond lengths and bond angles for
Table 3. IR data of ligands and complexes.
both compounds 8 and 9. Estimated standard deviations in paren-
Ligand
IR band [cm–1]
theses refer to the last significant digit.
ν(NH)
νas(SO2)[a]
νs(SO2)[b]
Δ(SO2)[c]
Compound 8
Compound 9
1
2
3
4
5
6
3258
3192
3260
3243
3217
3239
1303
1332
1306
1303
1307
1307
1162
1153
1156
1157
1169
1163
570
572
560
555
557
551
Bond length [Å]
Ru1–Cg1
Ru1–N1
Ru1–N2
Ru1–Cl1
S1–O2
S1–O1
S1–N2
S1–C111
N1–C1
N1–C9
N2–C8
1.6799(9)
2.0965(16)
2.1285(16)
2.4322(5)
1.4382(15)
1.4424(16)
1.6157(16)
1.768(2)
Ru1–Cg1
Ru1–N1
Ru1–N2
Ru1–Cl1
S1–O2
S1–O1
S1–N2
S1–C111
N1–C1
N1–C9
N2–C8
1.6666(7)
2.0852(14)
2.1236(13)
2.3981(5)
1.4392(13)
1.4496(12)
1.6146(14)
1.7774(17)
1.330(2)
Complex
νas(SO2)[a]
νs(SO2)[b]
Δ(SO2)[c]
7
–
–
–
–
–
–
1315
1316
1316
1315
1316
1317
1145
1140
1139
1140
1139
1144
577
572
577
567
582
563
8
9
1.324(3)
1.373(3)
1.400(2)
10
11
12
1.377(2)
1.406(2)
Bond angle [°]
[a] νas: asymmetric stretching. [b] νs: symmetric stretching. [c] Δ:
bending.
Cg1–Ru1–Cl1
Cg1–Ru1–N1
Cg1–Ru1–N2
N1–Ru1–N2
N1–Ru1–Cl1
N2–Ru1–Cl1
O2–S1–O1
127.01(4)
131.54(5)
131.93(5)
76.86(6)
84.31(5)
87.46(5)
116.55(10)
107.43(9)
111.55(9)
107.18(10)
106.93(9)
106.70(9)
118.80(17)
125.07(14)
116.10(12)
118.75(13)
115.35(12)
125.75(9)
122.4(2)
Cg1–Ru1–Cl1
Cg1–Ru1–N1
Cg1–Ru1–N2
N1–Ru1–N2
N1–Ru1–Cl1
N2–Ru1–Cl1
O2–S1–O1
127.27(3)
130.32(4)
130.13(4)
77.10(5)
85.09(4)
90.18(4)
116.60(8)
107.34(7)
112.02(7)
108.86(8)
106.36(8)
105.03(7)
119.04(15)
125.18(11)
115.69(11)
119.50(11)
114.30(10)
126.19(8)
122.31(16)
Catalytic Studies
As the starting point, the performances of the catalysts
in the TH were screened by using acetophenone as a model
substrate and we screened the influence of the base. NaOH
and KOH are known to yield better conversions than
K2CO3 and KOtBu in TH reactions.[36,49] The stronger the
base, the higher the general conversion rankings: KOH Ͼ
NaOH Ͼ KOtBu Ͼ K2CO3. Indeed, the TH of acetophen-
one catalyzed by 10 led to better results when using KOH,
and the reaction reached 97% conversion within 120 min at
O2–S1–N2
O1–S1–N2
O2–S1–N2
O1–S1–N2
O2–S1–C111
O1–S1–C111
N2–S1–C111
C1–N1–C9
C1–N1–Ru1
C9–N1–Ru1
C8–N2–S1
C8–N2–Ru1
S1–N2–Ru1
N1–C1–C2
O2–S1–C111
O1–S1–C111
N2–S1–C111
C1–N1–C9
C1–N1–Ru1
C9–N1–Ru1
C8–N2–S1
C8–N2–Ru1
S1–N2–Ru1
N1–C1–C2
a
substrate/catalyst/base (S/C/base) molar ratio of
1:0.002:10 (Figure 4). In the absence of base, no TH was
1
Table 2. H NMR and 13C NMR spectroscopic data of the ligands and complexes.
Ligand
δ(1H)/δ(13C) [ppm]
p-C(CH3)3
Ha
Hb
Hc
–
NH
9.31
p-OCH3
p-CH2CH2CH3
1
7.86
1.24 (1H)
–
–
35.0, 30.9 (13C)
2
3
7.80
8.80
6.99
8.20
–
–
10.02
11.66
–
–
3.74 (1H)/56.1
–
(13C)
–
0.84, 3.12, 1.40 (1H)
45.9, 24.0, 8.7 (13C)
4
5
6
7.83
7.86
8.03
7.80
7.79
7.86
–
7.88
–
11.00
11.21
10.94
–
–
–
–
–
–
–
–
–
Complex Hk
Hx
Hy
Hl
Hm
p-C(CH3)3
p-OCH3
p-CH2CH2CH3
7
2.37
6.29
5.70
2.62
0.95–1.07
1.24 (1H)
–
–
34.8, 31.1 (13C)
8
9
2.36
2.34
6.26
6.24
5.67
5.86
2.62
2.61
0.92–1.08
0.92–1.07
–
–
3.72 (1H)/55.3
–
(13C)
–
0.83, 3.10, 1.37 (1H)
46.1, 24.1, 8.7 (13C)
10
11
12
2.36
2.37
2.36
6.23
6.26
6.23
5.67
5.69
5.68
2.63
2.62
2.63
0.94–1.09
0.93–1.08
0.94–1.09
–
–
–
–
–
–
–
–
–
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observed. Therefore, KOH was selected as the base in all
subsequent studies.
Figure 4. Effect of various bases in the TH of acetophenone cata-
lyzed by 10 (0.2 mol-%) in 2-propanol at 82 °C.
A variety of ketones was transformed into the corre-
sponding secondary alcohols. Typical results are shown in
Figure 5. The transformation of 4-chloroacetophenone was
the fastest, and complete conversion to the corresponding
alcohol was observed after 120 min under the selected op-
erating conditions (Figure 5, b). Among the tested catalysts,
complexes 8, 10, and 12 were more efficient than complexes
7, 9, and 11.
We also examined the TH of acetophenone at a S/C/base
molar ratio of 1:0.001:10 (Figure 6). The results of the cata-
lytic experiments show once again that complexes 10 and
12 are highly efficient. The highest measured turnover fre-
quency (TOF) was in the 734–575 h–1 range for a S/C molar
ratio of 1:0.001 at 20 min (Table 4).
Conclusions
In summary, we have reported the preparation and char-
acterization of sulfonamide ligands 1–6 and their neutral
half-sandwich sulfonamido–RuII complexes 7–12. We have
also reported the catalytic activity of these complexes in the
TH of some acetophenone derivatives with the use of 2-
propanol in the presence of base. Complexes 10 and 12 are
the most active complexes. The procedure is simple and ef-
ficient towards various aryl ketones. The catalyst efficiency
depends not only on the ligand but also on the aromatic
ketone substituent. Electron-withdrawing groups intro-
duced at the para position of acetophenone accelerate the
transformation, whereas electron-donating groups slow it
down. Likewise, the presence of electron-withdrawing
groups on the sulfonamido ring has a beneficial effect. The
catalytic activity decreases in the order 10 Ͼ 12 Ͼ 8 Ͼ 7 Ͼ
9 Ͼ 11, and the best results are obtained in the presence
of the Cl and CF3 substituents at the para position to the
sulfonamido aryl group. Ruthenium(II) arene complexes are
widely used in the TH of ketones. When examined in the
context of the literature, it is clear that the half-sandwich
sulfonamido–RuII complexes used herein show good effi-
ciency in TH reactions.[59–73]
Figure 5. Catalytic activity as shown by the %conversion versus
time plot for the TH of (a) acetophenone, (b) 4-chloroacetophen-
one, and (c) 4-methylacetophenone catalyzed by 7–12 in 2-prop-
anol. Conditions: ketone/Ru/KOH = 1:0.002:10, T = 82 °C.
Experimental Section
Materials and Methods: All reagents and solvents were obtained
from commercial suppliers and used without any additional purifi-
cation. NMR spectra were recorded in 5 mm tubes at 297 K with
a Bruker Avance III 400 NMR spectrometer at 400 (for 1H) and
100.56 MHz (for 13C). Signals are quoted relative to tetramethylsil-
ane (δ = 0.00 ppm). Abbreviations used for the NMR resonances
are: br. broad, s singlet, d doublet, t triplet, m multiplet. Infrared
spectra were measured with a Perkin–Elmer Spectrum 400 FTIR
system and recorded by using a universal ATR sampling accessory
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slow addition of a solution of triethylamine (20 mmol) in THF
(5 mL) followed by a solution of 8-aminoquinoline (10 mmol) in
THF (5 mL) gave rise to the immediate precipitation of a white
solid [HCl·N(C2H5)3]. After being stirred for 12 h at room tempera-
ture, the solid was removed by filtration by using a fine-sintered-
glass filter. Then, the solvent was completely removed under re-
duced pressure. The crude product was used without further purifi-
cation. An analytically pure sample was obtained by recrystalli-
zation from chloroform/diethyl ether (15 mL, 1:3, v/v; Figure 1).
N-Quinoline-8-yl-4-tert-butylbenzenesulfonamide (1): Yield 85%.
orange solid, m.p. 155–157 °C. 1H NMR (CDCl3): δ = 1.24 [s, 9
H, -C(CH3)3], 7.37–7.48 (m, 4 H, -H2-5), 7.86 (dd, J = 4, 4 Hz, 4
H, -Ha-b), 8.13 (d, J = 8 Hz, 1 H, -H1), 8.77 (d, J = 8 Hz, 1 H,
-H6), 9.31 (br. 1 H, -NH) ppm. 13C NMR (CDCl3): δ = 30.9
[-C(CH3)3], 35.0 [-C(CH3)3], 115.1 (aryl-C), 121.9 (aryl-C), 122.0
(aryl-C), 125.9 (aryl-C), 127.0 (aryl-C), 128.2 (aryl-C), 133.8 (aryl-
C), 136.4 (aryl-C), 136.6 (aryl-C), 138.2 (aryl-C), 148.4 (aryl-C),
Figure 6. Catalytic activity as shown by the %conversion versus
time plot for the TH of acetophenone catalyzed by 7–12 in 2-prop-
anol at a S/C/KOH ratio of 1:0.001:10, T = 82 °C.
Table 4. Initial TOF for the TH of various ketones catalyzed by 7–12.[a]
[a] Acetophenone/Ru molar ratio.
within the range 550–4000 cm–1. Melting points were determined
in open capillary tubes with a digital Electrothermal 9100 melting
point apparatus. GC measurements for catalytic experiments were
performed by using Fisons 8000 Series instrument equipped with
a DB-1MS column (30 mϫ0.32 mmϫ0.25 m) and Younglin Acme
6100, OPTIMA 5 MS column (30mϫ0.32mmϫ0.25 m).
148.5 (aryl-C), 156.7 (aryl-C) ppm. IR: ν = 3258 (–NH), 3078,
˜
2962, 2905, 2869, 1623, 1595, 1579, 1505, 1471, 1436, 1414, 1397,
1378, 1362, 1336, 1303 (–SO2), 1266, 1236, 1206, 1194, 1162
(–SO2), 1139, 1112, 1086, 1057, 1029, 1013, 984, 972, 962, 922, 894,
851, 824, 803, 792, 749, 734, 645, 637, 626, 600, 570 (–SO2), 548,
515, 478, 466 cm–1. C19H20N2O2S (340.3): calcd. for C 67.03, H
5.92, N 8.23, O 9.40, S 9.42; found C 67.15, H 5.84, N 8.18, S 9.47.
TOF = mol of product/(mol of catalyst)ϫ(hour), measured on the
basis of the conversion at 20 min for entries 1–18 and at 30 min for
entries 19–24. Conditions are given in the legends of Figures 5 and
6.
N-Quinoline-8-yl-4-methoxybenzenesulfonamide (2): Yield 78%,
brown solid, m.p. 145–147 °C. 1H NMR (DMSO): δ = 3.74 (s, 3
H, -OCH3), 6.99 (d, J = 8 Hz, 2 H, -Hb), 7.55–7.77 (m, 4 H, -H2-
5), 7.80 (d, J = 8 Hz, 2 H, -Ha), 8.55 (d, J = 8 Hz, 1 H, -H1), 8.95
(d, J = 8 Hz, 1 H, -H6), 10.02 (br. 1 H, -NH) ppm. 13C NMR
(DMSO): δ = 56.1 (-OCH3), 114.8 (aryl-C), 119.7 (aryl-C), 122.9
(aryl-C), 124.3 (aryl-C), 127.8 (aryl-C), 128.9 (aryl-C), 129.8 (aryl-
C), 130.9 (aryl-C), 132.9 (aryl-C), 138.0 (aryl-C), 139.4 (aryl-C),
General Procedure for the Synthesis of Ligands (L) 1–6: N-(Quinol-
ine-8-yl-aryl)benzenesulfonamides 1–6 were prepared by modifying
a published procedure.[44] A 50 mL Schlenk tube containing a mag-
netic stirring bar was charged with a solution of the suitable benz-
enesulfonyl chloride derivative (10 mmol) in THF (10 mL). The
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149.1 (aryl-C), 163.1 (aryl-C) ppm. IR: ν = 3192 (–NH), 3192
(aryl-C) ppm. IR: ν = 3239 (–NH), 3106, 3069, 3051, 2980, 2947,
˜
˜
(–NH), 3045, 2971, 2872, 2776, 2731, 1629, 1590, 1576, 1543, 1489, 1603, 1581, 1505, 1473, 1435, 1403, 1371, 1321, 1307 (–SO2), 1255,
1465, 1436, 1425, 1408, 1375, 1347, 1332 (–SO2), 1310, 1298, 1285, 1238, 1163 (–SO2), 1134, 1104, 1086, 1061, 1030, 1007, 972, 922,
1256, 1220, 1206, 1178, 1153 (–SO2), 1138, 1113, 1089, 1061, 1025, 830, 795, 759, 711, 656, 634, 603, 591, 575, 551 (–SO2), 521,
1006, 974, 935, 924, 909, 885, 849, 828, 803, 779, 768, 741, 698,
492 cm–1. C16H11F3N2O2S (353.8): calcd. for C 54.54, H3.15, F
638, 627, 605, 572 (–SO2), 555, 538, 516, 500, 484, 466 cm–1. 16.18, N 7.95, O 9.08, S 9.10; found C 54.42, H 3.21, N 7.81, S
C16H14N2O3S (314.2): calcd. for C 61.13, H 4.49, N 8.91, O 15.27,
S 10.20; found C 61.19, H 4.39, N8.81, S 10.11.
9.13.
General Procedure for the Synthesis of [(p-cymene)RuLCl] 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 stirred for 12 h
N-Quinoline-8-yl-4-n-propylbenzenesulfonamide (3): Yield 82%,
light-brown solid, m.p. 120–122 °C. 1H NMR (CDCl3): δ = 0.84 (t,
J
= 8 Hz, 2 H, -CH2CH2CH3), 1.40 (t, J = 8 Hz, 3 H,
-CH2CH2CH3), 3.12 (m, 2 H, -CH2CH2CH3), 7.14–7.89 (m, 4 H, at 60 °C. The volatiles were removed under reduced pressure. The
-H2-5), 8.20 (d, J = 8 Hz, 2 H, -Hb), 8.74 (d, J = 8 Hz, 1 H, -H1), residue was washed with diethyl ether (20 mL) and dried under
8.80 (d, J = 8 Hz, 2 H, -Ha), 8.96 (d, J = 8 Hz, 1 H, -H6), 11.66 vacuum. The desired products were recrystallized from MeOH to
(br. 1 H, -NH) ppm. 13C NMR (CDCl3): δ = 8.7 (-CH2CH2CH3),
24.0 (-CH2CH2CH3), 45.9 (-CH2CH2CH3), 116.5 (aryl-C), 120.3
(aryl-C), 121.8 (aryl-C), 122.4 (aryl-C), 125.9 (aryl-C), 127.3 (aryl-
C), 128.3 (aryl-C), 128.9 (aryl-C), 131.3 (aryl-C), 133.3 (aryl-C),
give orange or dark red-colored microcrystals (Figure 2).
[(N-Quinoline-8-yl-4-tert-butylbenzenesulfonamido)(p-cymene)chloro-
ruthenium(II)] (7): Yield 72 %, orange microcrystals, m.p. 291–
1
292 °C. H NMR (CDCl3): δ = 0:95 and 1:07 (d and d, J = 8 Hz,
136.6 (aryl-C), 147.8 (aryl-C), 148.4 (aryl-C) ppm. IR: ν = 3260
˜
6 H, -Hm), 1.24 [s, 9 H, -C(CH3)3], 2.37 (s, 3 H, -Hk), 2.62 (m, 1
H, -Hl), 5.70 (d, J = 4 Hz, 2 H, -Hy), 6.29 (d, J = 4 Hz, 2 H, -Hx),
7.01–7.44 (m, 4 H, -H2-5), 8.07 (d, J = 8 Hz, 1 H, -H1), 8.15 (dd, J
= 4, 4 Hz, 4 H, -Ha-b), 9.10 (d, J = 8 Hz, 1 H, -H6) ppm. 13C NMR
(CDCl3): δ = 19.3 (-CH3), 22.1 [-CH(CH3)2], 30.9 [-CH(CH3)2],
31.1 [-C(CH3)3], 34.8 [-C(CH3)3], 82.3 (aryl-C), 84.6 (aryl-C), 86.2
(aryl-C), 104.5 (aryl-C), 115.7 (aryl-C), 118.0 (aryl-C), 121.9 (aryl-
C), 125.4 (aryl-C), 128.3 (aryl-C), 129.0 (aryl-C), 129.5 (aryl-C),
137.8 (aryl-C), 137.9 (aryl-C), 144.7 (aryl-C), 147.4 (aryl-C), 151.1
(–NH), 3068, 2959, 2932, 2866, 2605, 2498, 1662, 1623, 1593, 1543,
1504, 1471, 1446, 1435, 1429, 1408, 1378, 1367, 1330, 1306 (–SO2),
1248, 1237, 1223, 1184, 1156 (–SO2), 1119, 1112, 1086, 1058, 1029,
1018, 999, 970, 921, 883, 844, 829, 817, 806, 795, 758, 728, 690,
679, 637, 601, 575, 560 (–SO2), 535, 526, 485, 470 cm–1.
C18H18N2O2S (326.3): calcd. for C 66.23, H 5.56, N 8.58, O 9.80,
S 9.82; found C 66.35, H 5.61, N 8.49, S 9.95.
N-Quinoline-8-yl-4-chlorobenzenesulfonamide (4): Yield 81%,
brown solid, m.p. 110–112 °C. 1H NMR (CDCl3): δ = 7.30–7.49
(aryl-C), 154.6 (aryl-C) ppm. IR: ν = 3055, 2960, 2906, 2869, 1639,
˜
(m, 4 H, -H2-5), 7.80 (d, J = 8 Hz, 2 H, -Hb), 7.83 (d, J = 8 Hz, 2 1597, 1570, 1535, 1530, 1502, 1462, 1432, 1376, 1365, 1315 (–SO2),
H, -Ha), 8.10 (d, J = 8 Hz, 1 H, -H1), 8.74 (d, J = 8 Hz, 1 H, -H6), 1298, 1285, 1273, 1261, 1212, 1204, 1190, 1145 (–SO2), 1107, 1081,
11.00 (br. 1 H, -NH) ppm. 13C NMR (CDCl3): δ = 115.4 (aryl-C), 1057, 1047, 1015, 947, 905, 877, 868, 822, 803, 787, 749, 735, 712,
116.0 (aryl-C), 122.1 (aryl-C), 122.6 (aryl-C), 126.8 (aryl-C), 127.6
(aryl-C), 128.3 (aryl-C), 128.6 (aryl-C), 129.2 (aryl-C), 133.4 (aryl-
6 9 0 , 6 6 5 , 6 4 9 , 6 2 3 , 5 7 7 ( – S O 2 ) , 5 4 9 , 5 2 3 , 4 7 0 c m– 1
C29H33ClN2O2RuS (609.9): calcd. for C 56.90, H 5.76, Cl 5.79, N
.
C), 136.3 (aryl-C), 139.4 (aryl-C), 148.9 (aryl-C) ppm. IR: ν = 3243 4.58, O 5.23, Ru 16.51, S 5.24; found C 56.80, H 5.92, N 4.57, S
˜
(–NH), 3089, 3019, 2978, 2947, 1618, 1581, 1504, 1470, 1435, 1412, 5.23.
1396, 1366, 1334, 1303 (–SO2), 1278, 1258, 1233, 1188, 1174, 1157
[(N-Quinoline-8-yl-4-methoxybenzenesulfonamido)(p-cymene)chloro-
(–SO2), 1135, 1122, 1083, 1057, 1031, 1005, 977, 920, 849, 822, 805,
ruthenium(II)] (8): Yield 82%, dark red microcrystals, m.p. 194–
794, 786, 751, 705, 647, 620, 574, 555 (–SO2), 523, 480, 459 cm–1.
C15H11ClN2O2S (318.7): calcd. for C 56.52, H 3.48, Cl 11.12, N
8.79, O 10.04, S 10.06; found C 56.43, H 3.56, N 8.67, S 10.10.
1
196 °C. H NMR (CDCl3): δ = 0:92 and 1:08 (d and d, J = 8 Hz,
6 H, -Hm), 2.36 (s, 3 H, -Hk), 2.62 (m, 1 H, -Hl), 3.72 (s, 3 H,
-OCH3), 5.67 (d, J = 4 Hz, 2 H, -Hy), 6.26 (d, J = 4 Hz, 2 H, -Hx),
N-Quinoline-8-yl-benzenesulfonamide (5): Yield 75%, brown solid,
6.77 (d, J = 8 Hz, 2 H, -Hb), 7.55–7.77 (m, 4 H, -H2-5), 8.06 (d, J
m.p. 90–92. 1H NMR (CDCl3): δ = 7.32–7.43 (m, 4 H, -H2-5), 7.79 = 8 Hz, 1 H, -H1), 8.16 (d, J = 8 Hz, 2 H, -Ha), 9.10 (d, J = 8 Hz,
(t, J = 8 Hz, 2 H, -Hb), 7.86 (d, J = 8 Hz, 2 H, -Ha), 7.88 (t, J =
8 Hz, 1 H, -Hc), 8.07 (d, J = 8 Hz, 1 H, -H1), 8.72 (d, J = 8 Hz, 1
1 H, -H6) ppm. 13C NMR (CDCl3): δ = 19.3 (-CH3), 22.1
[-CH(CH3)2], 31.0 [-CH(CH3)2], 55.3 (-OCH3), 80.6 (aryl-C), 82.3
H, -H6), 11.21 (br., 1 H, NH) ppm. 13C NMR (CDCl3): δ = 115.0 (aryl-C), 84.4 (aryl-C), 86.2 (aryl-C), 113.5 (aryl-C), 115.8 (aryl-C),
(aryl-C), 122.0 (aryl-C), 122.3 (aryl-C), 125.9 (aryl-C), 126.8 (aryl-
C), 127.2 (aryl-C), 128.2 (aryl-C), 128.9 (aryl-C), 129.8 (aryl-C),
117.9 (aryl-C), 121.9 (aryl-C), 128.9 (aryl-C), 129.5 (aryl-C), 130.6
(aryl-C), 132.6 (aryl-C), 137.8 (aryl-C), 144.7 (aryl-C), 147.4 (aryl-
132.9 (aryl-C), 136.3 (aryl-C), 139.3 (aryl-C), 148.5 (aryl-C) ppm. C), 151.2 (aryl-C), 161.8 (aryl-C) ppm. IR: ν = 3091, 3047, 2962,
˜
IR: ν = 3217 (–NH), 2980, 2947, 2883, 1618, 1597, 1505, 1472,
2904, 2875, 1642, 1592, 1568, 1534, 1498, 1466, 1440, 1412, 1387,
1373, 1316 (–SO2), 1292, 1285, 1274, 1252, 1216, 1191, 1182, 1157,
1140 (–SO2), 1134, 1111, 1082, 1059, 1045, 1026, 1018, 1008, 990,
943, 902, 863, 840, 818, 805, 790, 779, 759, 720, 692, 660, 628, 590,
572 (–SO2), 555, 527, 473 cm–1. C26H27ClN2O3RuS (583.9): calcd.
for C 53.28, H 4.99, Cl 6.05, N 4.78, O 8.19, Ru 17.24, S 5.47;
found C 53.35, H 4.87, N 4.69, S 5.55.
˜
1446, 1431, 1406, 1398, 1371, 1358, 1333, 1307 (–SO2), 1231, 1169
(–SO2), 1123, 1086, 1072, 1057, 1033, 1016, 997, 952, 926, 852, 820,
805, 786, 750, 726, 685, 666, 611, 584, 568, 557 (–SO2), 518,
462 cm–1. C15H12N2O2S (284.2): calcd. for C 63.36, H 4.25, N 9.85,
O 11.25, S 11.28; found C 63.47, H 4.16, N 9.78, O 11.34 S 11.24.
N-Quinoline-8-yl-4-(trifluoromethyl)benzenesulfonamide (6): Yield
1
71%, brown solid, m.p. 128–130 °C. H NMR (CDCl3): δ = 7.42–
[(N-Quinoline-8-yl-4-n-propylbenzenesulfonamido)(p-cymene)-
7.63 (m, 4 H, -H2-5), 7.86 (d, J = 8 Hz, 2 H, -Hb), 8.03 (d, J = chlororuthenium(II)] (9): Yield 76%, dark red microcrystals, m.p.
8 Hz, 2 H, -Ha), 8.11 (d, J = 8 Hz, 1 H, -H1), 8.75 (d, J = 8 Hz, 1 247–248 °C. 1H NMR (CDCl3): δ = 0.83 (t, J = 8 Hz, 2 H,
H, -H6), 10.94 (br. 1 H, -NH) ppm. 13C NMR (CDCl3): δ = 115.5 -CH2CH2CH3), 0.92 and 1.07 (d and d, J = 8 Hz, 6 H, -Hm), 1.37
(aryl-C), 116.0 (aryl-C), 122.2 (aryl-C), 122.9 (aryl-C), 124.4 (aryl-
(t, J = 8 Hz, 3 H, -CH2CH2CH3), 2.34 (s, 3 H, -Hk), 2.61 (m, 1
C), 126–126.2 (-CF3), 126.6 (aryl-C), 126.8 (aryl-C), 127.7 (aryl-C), H, -Hl), 3.10 (m, 2 H, -CH2CH2CH3), 5.86 (d, J = 4 Hz, 2 H,
128.3 (aryl-C), 133.1 (aryl-C), 136.4 (aryl-C), 138.5 (aryl-C), 148.9
-Hy), 6.24 (d, J = 4 Hz, 2 H, -Hx), 6.96–7.20 (m, 4 H, -H2-5), 7.37
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(d, J = 8 Hz, 2 H, -Hb), 8.04 (d, J = 8 Hz, 1 H, -H1), 8.11 (d, J =
8 Hz, 2 H, -Ha), 9.10 (d, J = 8 Hz, 1 H, -H6) ppm. 13C NMR
30.9 [-CH(CH3)2], 80.7 (aryl-C), 82.4 (aryl-C), 84.4 (aryl-C), 85.9
(aryl-C), 116.6 (aryl-C), 117.9 (aryl-C), 122.2 (aryl-C), 125.3–125.5
(CDCl3): δ = 8.7 (-CH2CH2CH3), 19.3 (-CH3), 22.3 [-CH(CH3)2], (-CF3), 126.5 (aryl-C), 126.6 (aryl-C), 128.9 (aryl-C), 129.6 (aryl-
24.1 (-CH2CH2CH3), 30.9 [-CH(CH3)2], 46.1 (-CH2CH2CH3), 80.6 C), 133.0 (aryl-C), 137.9 (aryl-C), 138.7 (aryl-C), 139.3 (aryl-C),
(aryl-C), 82.3 (aryl-C), 84.5 (aryl-C), 86.1 (aryl-C), 115.8 (aryl-C),
117.9 (aryl-C), 121.9 (aryl-C), 128.4 (aryl-C), 128.5 (aryl-C), 128.9
(aryl-C), 129.5 (aryl-C), 137.8 (aryl-C), 138.1 (aryl-C), 144.7 (aryl-
144.6 (aryl-C), 151.6 (aryl-C) ppm. IR: ν = 3035, 2967, 2929, 2872,
˜
2812, 1607, 1573, 1538, 1505, 1468, 1402, 1379, 1317 (–SO2), 1294,
1235, 1215, 1186, 1160, 1144 (–SO2), 1129, 1107, 1086, 1061, 1016,
949, 910, 876, 852, 832, 821, 806, 793, 781, 770, 759, 736, 708, 666,
C), 146.2 (aryl-C), 147.4 (aryl-C), 151.3 (aryl-C) ppm. IR: ν = 3049,
˜
2977, 2953, 2926, 2868, 2851, 1595, 1569, 1531, 1505, 1464, 1423,
632,
609,
563
(–SO2),
541,
524,
504,
472 cm–1.
1398, 1378, 1363, 1316 (–SO2), 1289, 1269, 1235, 1214, 1201, 1189, C26H24ClF3N2O2RuS (621.9): calcd. for C 50.20, H 3.89, Cl 5.70,
1158, 1136 (–SO2), 1114, 1081, 1044, 1019, 990, 947, 905, 872, 842,
825, 806, 793, 785, 761, 675, 652, 635, 605, 589, 577, 540, 528, 516,
505, 465 cm–1. C28H31ClN2O2RuS (595.9): calcd. for C 56.22, H
5.56, Cl 5.93, N 4.68, O 5.35, Ru 16.90, S 5.36; found C 56.31, H
5.48, N 4.60, S 5.40.
F 9.16, N 4.50, O 5.14, Ru 16.25, S 5.15; found C 50.12, H 3.96,
N 4.40, S 5.22.
X-ray Structural Analyses: Single crystals of compounds 8 and 9
were mounted under inert perfluoropolyether at the tip of a glass
fiber and cooled in the cryostream of a Bruker APEX2 CCD dif-
fractometer. The structures were solved by direct methods
(SIR97[53]) and refined by least-squares procedures on F2 by using
SHELXL-97.[54] All H atoms attached to carbon atoms were intro-
duced in the calculation in idealized positions and treated as riding
models. The drawing of the molecules was realized with the help
of ORTEP32.[55] Crystal data and refinement parameters are shown
in Table 5.
[(N-Quinoline-8-yl-4-chlorobenzenesulfonamido)(p-cymene)chloro-
ruthenium(II)] (10): Yield 83%, dark red microcrystals, m.p. 171–
1
172 °C. H NMR (CDCl3): δ = 0.94 and 1.09 (d and d, J = 8 Hz,
6 H, -Hm), 2.36 (s, 3 H, -Hk), 2.63 (m, 1 H, -Hl), 5.67 (d, J = 4 Hz,
2 H, -Hy), 6.23 (d, J = 4 Hz, 2 H, -Hx), 7.03–7.28 (m, 4 H, -H2-5),
7.36 (d, J = 8 Hz, 2 H, -Hb), 8.10 (d, J = 8 Hz, 1 H, -H1), 8.19 (d,
J = 8 Hz, 2 H, -Ha), 9.12 (d, J = 8 Hz, 1 H, -H6) ppm. 13C NMR
(CDCl3): δ = 19.3 (-CH3), 22.2–22.3 [-CH(CH3)2], 31.0 [-CH(CH3)
2], 80.7 (aryl-C), 82.4 (aryl-C), 84.3 (aryl-C), 85.9 (aryl-C), 116.4
(aryl-C), 117.9 (aryl-C), 122.1 (aryl-C), 127.7 (aryl-C), 128.5 (aryl-
C), 128.9 (aryl-C), 129.5 (aryl-C), 130.2 (aryl-C), 137.5 (aryl-C),
137.9 (aryl-C), 139.4 (aryl-C), 144.7 (aryl-C), 151.5 (aryl-C) ppm.
Table 5. Crystal data for 8 and 9.
8
9
Empirical formula
Formula weight
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C26H27ClN2O3RuS
584.08
180(2)
0.71073
monoclinic
P21/n
14.4087(17)
11.6057(14)
16.2028(19)
90.0
C28H31ClN2O2RuS
596.13
180(2)
0.71073
monoclinic
P21/c
10.5377(12)
13.6881(14)
17.987(2)
90.0
IR: ν = 3055, 3010, 2960, 2869, 1572, 1532, 1532, 1502, 1465, 1446,
˜
1422, 1392, 1377, 1315 (–SO2), 1298, 1278, 1270, 1233, 1214, 1189,
1173, 1161, 1140 (–SO2), 1111, 1080, 1044, 1031, 1013, 1005, 985,
965, 946, 905, 868, 833, 821, 805, 792, 781, 748, 708, 693, 666,
646, 614, 587, 567 (–SO2), 541, 524, 501, 480, 470, 461, 455 cm–1.
C25H24Cl2N2O2RuS (588.4): calcd. for C 50.85, H 4.44, Cl 12.01,
N 4.74, O 5.42, Ru 17.12, S 5.43; found C 50.91, H 4.40, N 4.78,
S 5.49.
β [°]
γ [°]
116.146(2)
90.0
2432.2(5)
4
95.771(5)
90.0
2581.3(5)
4
1.534
0.821
[(N-Quinoline-8-yl-benzenesulfonamido)(p-cymene)chlororuthen-
ium(II)] (11): Yield 83%, dark red microcrystals, m.p. 256–257 °C.
1H NMR (CDCl3): δ = 0.93 and 1.08 (d and d, J = 8 Hz, 6 H,
-Hm), 2.37 (s, 3 H, -Hk), 2.62 (m, 1 H, -Hl), 5.69 (d, J = 4 Hz, 2
Volume [Å3]
Z
Density (calcd.) [Mgm–3] 1.595
Abs. coefficient [mm–1]
F(000)
0.872
1192
0.50ϫ0.45ϫ0.25
2.25 to 30.03
49026
H, -Hy), 6.26 (d, J = 4 Hz, 2 H, -Hx), 6.98–7.41 (m, 4 H, -H2-5
,
1224
Crystal size [mm3]
θ range [°]
0.48ϫ0.48ϫ0.10
1.87 to 29.24
21457
-Hb,c), 8.06 (d, J = 8 Hz, 1 H, -H1), 8.23 (d, J = 8 Hz, 2 H, -Ha),
9.11 (d, J = 8 Hz, 1 H, -H6) ppm. 13C NMR (CDCl3): δ = 19.3
(-CH3), 22.1, 22.3 [-CH(CH3)2], 30.9 [-CH(CH3)2], 80.5 (aryl-C),
82.3 (aryl-C), 84.4 (aryl-C), 86.1 (aryl-C), 116.0 (aryl-C), 117.9
(aryl-C), 121.9 (aryl-C), 128.4 (aryl-C), 128.6 (aryl-C), 128.9 (aryl-
C), 129.5 (aryl-C), 131.3 (aryl-C), 137.8 (aryl-C), 140.9 (aryl-C),
Reflns collected
Independent reflns (Rint
Completeness [%]
Absorption correction
Max./min. transmission
Refinement method
)
7061 (0.0242)
99.2
multiscan
0.7462/0.6219
F2
6964 (0.0243)
99.1
multiscan
0.7458/0.6462
F2
144.7 (aryl-C), 147.2 (aryl-C), 151.3 (aryl-C) ppm. IR: ν = 3058,
˜
2964, 2935, 2870, 1570, 1531, 1503, 1475, 1464, 1445, 1423, 1378,
1316 (–SO2), 1298, 1290, 1274, 1234, 1214, 1189, 1176, 1165, 1139
(–SO2), 1112, 1087, 1044, 1028, 1010, 961, 946, 933, 898, 868, 850,
824, 817, 805, 795, 783, 777, 753, 714, 692, 662, 637, 614, 582
(–SO2), 565, 539, 524, 502, 473, 463 cm–1. C25H25ClN2O2RuS
(553.9): calcd. for C 54.00, H 4.89, Cl 6.38, N 5.04, O 5.75, Ru
18.18, S 5.77; found C 54,12, H 4.81, N 5.14, S 5.69.
Data/restraints/parameters 7061/0/311
6964/0/320
1.059
0.0250, 0.0581
0.0298, 0.0604
0.477 and –0.496
Goodness-of-fit on F2
R1, wR2 [IϾ2σ(I)]
1.062
0.0292, 0.0624
0.0404, 0.0706
1.066 and –0.586
R1, wR2 (all data)
Residual density [eÅ–3]
CCDC-925980 (for 8) and -925981 (for 9) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
{[N-Quinoline-8-yl-4-(trifluoromethyl)benzenesulfonamido](p-cym-
ene)chlororuthenium(II)} (12): Yield 83%, dark red microcrystals,
1
m.p. 245–247 °C. H NMR (CDCl3): δ = 0.94 and 1.09 (d and d,
J = 8 Hz, 6 H, -Hm), 2.36 (s, 3 H, -Hk), 2.63 (m, 1 H, -Hl), 5.68 (d,
J = 4 Hz, 2 H, -Hy), 6.23 (d, J = 4 Hz, 2 H, -Hx), 7.05–7.41 (m, 4
H, -H2-5), 7.55 (d, J = 8 Hz, 2 H, -Hb), 8.10 (d, J = 8 Hz, 1 H,
Acknowledgments
-H1), 8.37 (d, J = 8 Hz, 2 H, -Ha), 9.12 (d, J = 8 Hz, 1 H, -H6) Financial support granted by Erciyes University (ERUBAP) (FBY-
ppm. 13C NMR (CDCl3): δ = 19.3 (-CH3), 22.1–22.3 [-CH(CH3)2], 12-3909, ID: 3909) is acknowledged.
Eur. J. Inorg. Chem. 2013, 3224–3232
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Received: February 25, 2013
Published Online: May 14, 2013
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