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Electronic Supplementary Information
Aryl Appended Neutral and Cationic Half-sandwich Ruthenium(II)-NHC Complexes: Synthesis, Characterisation and Catalytic Applications
Mambattakkara Viji,a,b Nidhi Tyagi,a Neeraj Naithanic and Danaboyina Ramaiah*d
aPhotosciences and Photonics, Chemical Sciences and Technology Division CSIR-National Institute for Interdisciplinary Science and Technology, Trivandrum, 695 019, India
bAcademy of Scientific and Innovative Research (AcSIR), CSIR-NIIST Campus cAnalytical and Spectroscopy Division, Vikram Sarabhai Space Centre, Trivandrum 695 022, India
dCSIR-North East Institute of Science and Technology, Jorhat 785 006, Assam
E-mail: [email protected] or [email protected]
Si. No Contents Page
1
Figures S1-S12 show 1H and 13C NMR spectra of the complexes 1-6
S2-S13
2 Figure S13 shows the electrochemical properties of the complexes 1-6 S14
3 Figure S14 shows the thermograms of the complexes 1, 2, 4 and 5 S15
4 Figure S15 shows the GC traces of the transfer hydrogenation products S16-S17
5 Figures S16-S24 show the 1H NMR spectra of the products isolated S18-S26
6 Characterization of the transfer hydrogenation products S27-S29
7 Table S1 shows the crystallographic data and processing parameters for the complexes 1-4
S30
8 Table S2 shows the selected bond lengths and bond angles for the complexes 1-4
S31
9 Table S3 shows the comparative efficiency of transfer hydrogenation of acetophenone using various catalysts
S32
10 Table S4 shows the optimized energy levels of intermediates and molecules involved in the mechanism.
S32
11 Scheme S1 shows the possible mechanism for TH reactions S33
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017
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S2
Figure S1. 1H NMR spectrum of the complex 1 in CDCl3.
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S3
Figure S2. 13C NMR spectrum of the complex 1 in DMSO.
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S4
Figure S3. 1H NMR spectrum of the complex 2 in CDCl3.
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S5
Figure S4. 13C NMR spectrum of the complex 2 in DMSO.
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S6
Figure S5. 1H NMR spectrum of the complex 3 in CD3CN.
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S7
Figure S6. 13C NMR spectrum of the complex 3 in CD3CN.
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S8
Figure S7. 1H NMR spectrum of the complex 4 in CD3CN.
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S9
Figure S8. 13C NMR spectrum of the complex 4 in CD3CN.
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S10
Figure S9. 1H NMR spectrum of the complex 5 in CD3CN.
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S11
Figure S10. 13C NMR spectrum of the complex 5 in CD3CN.
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S12
Figure S11. 1H NMR spectrum of the complex 6 in CD3CN.
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S13
Figure S12. 13C NMR spectrum of the complex 6 in CD3CN.
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S14
1.6 1.2 0.8 0.4 0.0
‐8.0x10‐6
‐4.0x10‐6
0.0Current(A)
Potential(V)
A)
1.6 1.2 0.8 0.4 0.0
‐1.2x10‐5
‐8.0x10‐6
‐4.0x10‐6
0.0
Current(A)
Potential(V)
B)
1.6 1.2 0.8 0.4‐1.0x10‐5
0.0
1.0x10‐5
2.0x10‐5
Current(A)
Potential(V)
C)
1.6 1.2 0.8 0.4‐2.0x10‐5
0.0
2.0x10‐5
4.0x10‐5
6.0x10‐5
Current(A)
Potential(V)
D)
1.6 1.2 0.8 0.4
‐1.0x10‐5
0.0
1.0x10‐5
2.0x10‐5
Current(A)
Potential(V)
E)
1.6 1.2 0.8 0.4‐2.0x10‐5
0.0
2.0x10‐5
Current(A)
Potential(V)
F)
Figure S13. Square-wave voltammograms of the complexes (1 mM each), A) 1 and B) 2 in
dichloromethane and cyclic voltammograms of the complexes, C) 3, D) 4, E) 5 and F) 6 in
acetonitrile at a scan rate of 100 mV/s.
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0 200 400 600 8000
50
100
0 200 400 600 8000
50
100C) D)
Weight(%)
Temperature(oC)
Weight(%)
Temperature(oC)
0 200 400 600 8000
50
100
0 200 400 600 8000
50
100
Weight(%)
Temperature(oC)
A)
Weight(%)
Temperature(oC)
B)
Figure S14. Theromograms of the complexes, A) 1, B) 2, C) 4 and D) 5.
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A) 1-Phenylethanol
3.25 3.50 3.75 4.00 4.25 4.50 4.75 5.00 5.25 5.50 5.75 6.00 6.25 6.50 6.75
0.5
1.0
1.5
(x10,000,000)TIC
40 50 60 70 80 90 100 110 1200
50
100
%
79107
7712243 51
10853 63 12391 10241 938768
B) 1-(4-Chlorophenyl)ethanol
5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5
1.0
2.0
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.00.0
25.0
50.0
%77 141
43113
15651 103 1217563 91 155127 219
C) 1-(4-Iodophenyl)ethanol
7.50 7.75 8.00 8.25 8.50 8.75 9.00 9.25 9.50 9.75 10.00 10.25
1.0
2.0
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.00
50
100
%
78
23343
24812151 103 205 23463 91 127 217152 176165
D) Diphenylmethanol
7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0
1.0
2.0
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.00
50
100
%
105
77 184
51 1651528263 115 1391289140 243
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E) (4-Bromophenyl)(phenyl)methanol
13.25 13.50 13.75 14.00 14.25 14.50 14.75 15.00 15.25 15.50 15.75 16.00 16.25 16.50
0.5
1.0
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.00.0
25.0
%10577
183
51 165 26215563 89 139115 247127 16840 233195
F) 1-(p-Tolyl)ethanol
4.75 5.00 5.25 5.50 5.75 6.00 6.25 6.50 6.75 7.00
0.5
1.0
1.5
2.0
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.00
50
100
%
12193
43 1367765 11551 10367 134 219
G) Di-p-tolylmethanol
10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 17.0
0.5
1.0
1.5
(x10,000,000)TIC
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 300.0 325.0 350.0 375.0 400.00.0
25.0
50.0
%119
91
21219765 77
16515241 128 388
H) 1-(3,4-Dimethoxyphenyl)ethanol
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5
0.5
1.0
1.5
(x10,000,000)TIC
40 50 60 70 80 90 100 110 120 130 140 150 160 170 1800
50
100
%
164
14991 13977103 18212143 6551 89 108 14041 75
Figure S15. GC traces A-H of the hydrogenation products.
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S18
Figure S16. 1H NMR spectrum of 1-phenylethanol in CD3CN.
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S19
Figure S17. 1H NMR spectrum of 1-(4-iodophenyl)ethanol in CD3CN.
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S20
Figure S18. 1H NMR spectrum of diphenylmethanol in CD3CN.
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S21
Figure S19. 1H NMR spectrum of (4-bromophenyl)(phenyl)methanol in CD3CN.
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S22
Figure S20. 1H NMR spectrum of 1-(4-chlorophenyl)ethanol in CD3CN.
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S23
Figure S21. 1H NMR spectrum of 1-(p-tolyl)ethanol in CD3CN.
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S24
Figure S22. 1H NMR spectrum of 1-(4-methoxyphenyl)ethanol in CD3CN.
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S25
Figure S23. 1H NMR spectrum of 1-(3,4,5-trimethoxyphenyl)ethanol in CD3CN.
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S26
Figure S24. 1H NMR spectrum of di-p-tolylmethanol in CD3CN.
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S27
Characterization data for isolated transfer hydrogenation products obtained in the presence of complex 1 as a representative example.
1-Phenylethanol[1]: Using the general procedure the transfer hydrogenation of 1-phenylethanone
was carried out in the presence of complex 1 at 80 oC for 2 h. Product obtained as colourless oily
liquid, Isolated yield (11 mg, 96%); 1H NMR (CD3CN, TMS, 500 MHz) δ (ppm) 1.36-1.38 (d,
3H), 3.24 (s, 1H), 4.76-4.81 (q, 1H), 7.21-7.22 (t, 1H), 7.30-7.36 (m, 4H); HRMS (ESI), m/z
Calcd for C8H10O 122.073; Found 123.081 (M +1).
1-(4-Chlorophenyl)ethanol[2]: Using the general procedure the transfer hydrogenation of 1-(4-
Chlorophenyl)ethanone was carried out in the presence of complex 1 at 80 oC for 2 h. Product
obtained as yellow oily liquid, Isolated yield (15.4 mg, 98%); 1H NMR (CD3CN, TMS, 500
MHz) δ (ppm) 1.35-1.36 (d, 3H), 3.28 (s, 1H), 4.76-4.81 (q, 1H), 7.33 (m, 4H); HRMS (ESI),
m/z Calcd for C8H9ClO 156.034; Found 156.015 (M+).
1-(4-Iodophenyl)ethanol[3]: Using the general procedure the transfer hydrogenation of 1-(4-
Iodophenyl)ethanone was carried out in the presence of complex 1 at 80 oC for 2 h. Product
obtained as off-white solid, Isolated yield (24 mg, 97%); 1H NMR (CD3CN, TMS, 500 MHz) δ
1.34-1.35 (d, 3H), 3.27 (s, 1H), 4.74-4.76 (q, 1H), 7.14-7.16 (d, 2H), 7.67-7.68 (d, 2H); HRMS
(ESI), m/z Calcd for C8H9IO 247.979; Found 248.061 (M+).
Diphenylmethanol[1]: Using the general procedure the transfer hydrogenation of benzophenone
was carried out in the presence of complex 1 at 80 oC for 2 h. Product obtained as white solid,
Isolated yield (17.3 mg, 94%); 1H NMR (CD3CN, TMS, 500 MHz) δ (ppm) 3.82 (s, 1H), 5.77 (d,
1H), 7.20-7.23 (t, 2H), 7.29-7.32 (t, 4H), 7.36-7.38 (d, 4H); HRMS (ESI), m/z Calcd for C13H12O
184.088; Found 184.943 (M+).
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S28
(4-Bromophenyl)(phenyl)methanol[4]: Using the general procedure the transfer hydrogenation
of (4-Bromophenyl)(penyl)methanone was carried out in the presence of complex 1 at 80 oC for
2 h. Product obtained as off-white solid, Isolated yield (23.5 mg, 89%); 1H NMR (CD3CN, TMS,
500 MHz) δ 3.88 (s, 1H), 5.74 (d, 1H), 7.29-7.36 (m, 7H), 7.46-7.47 (d, 2H); HRMS (ESI), m/z
Calcd for C13H11BrO 261.999 and 263.997; Found 262.989 (M+1) and 263.992.
1-(p-Tolyl)ethanol[1]: Using the general procedure the transfer hydrogenation of 1-(p-
Tolyl)ethanone was carried out in the presence of complex 1 at 80 oC for 3 h. Product obtained as
light yellow oily liquid, Isolated yield (12.6 mg, 92%); 1H NMR (CD3CN, TMS, 500 MHz) δ
(ppm) 1.34-1.35 (d, 3H), 2.30 (s, 3H), 3.1 (s, 1H), 4.74-4.76 (q, 1H), 7.13-7.14 (d, 2H), 7.22-7.24
(d, 2H); HRMS (ESI), m/z Calcd for C9H12O 136.088; Found 136.064 (M+).
1-(4-Methoxyphenyl)ethanol[5]: Using the general procedure the transfer hydrogenation of 1-(4-
Methoxyphenyl)ethanone was carried out in the presence of complex 1 at 80 oC for 3 h. Product
obtained as light brown oil, Isolated yield (13.4 mg, 88%); 1H NMR (CD3CN, TMS, 500 MHz) δ
(ppm) 1.36-1.37 (d, 3H), 3.07-3.08 (d 1H), 3.76 (s, 3H), 4.71-4.76 (q, 1H), 6.86-6.88 (m, 2H),
7.26-7.27 (m, 2H); HRMS (ESI), m/z Calcd for C9H12O2 152.083; Found 152.076 (M+).
Di-p-tolylmethanol[6]: Using the general procedure the transfer hydrogenation of Di-p-
tolylmethanone was carried out in the presence of complex 1 at 80 oC for 3 h. Product obtained
as off-white solid, Isolated yield (19.5 mg, 91%); 1H NMR (CD3CN, TMS, 500 MHz) δ 2.28 (s,
6H), 3.66 (s, 1H), 5.67-5.68 (d, 1H), 7.10-7.12 (d, 4H), 7.21-7.23 (d, 4H); HRMS (ESI), m/z
Calcd for C15H16O 212.120; Found 212.113 (M+).
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S29
Transfer hydrogenation of 1-(4-Chlorophenyl)ethanone in the presence of complex 1
A solution of complex 1(19.4 mg, 0.02 mmol, 2 mol%) in 20 mL of 2-propanol was
sonicated for 10-15 minutes. Then NaOH was (40 mg, 1 mmol) was added and preheated the
solution for 10 minutes. The substrate 1-(4-Chlorophenyl)ethanone (154 mg, 1 mmol) was then
added slowly and allowed the reaction mixture to reflux at 80 oC for 2 h. After completing the
reaction, the reaction mixture was passed through a small pad of silica and elute with hexane.
The solvent was evaporated to dryness to yield yellow oily liquid (142 mg, 91%), 1-(4-
Chlorophenyl)ethanol as the product. The product was characterized by spectral and analytical
techniques. 1H NMR (CD3CN, TMS, 500 MHz) δ (ppm) 1.35-1.36 (d, 3H), 3.28 (s, 1H), 4.76-
4.81 (q, 1H), 7.33 (m, 4H); 13C NMR (CD3CN, 125 MHz) δ (ppm) 24.5, 68.1, 126.7, 127.8,
131.5, 145.5.
REFERENCES
[1]. P. N. Liu, K. D. Ju and C. P. Lau, Adv. Synth. Catal., 2011, 353, 275.
[2]. Y. Xu, G. C. Clarkson, G. Docherty, C. L. North, G. Woodward and M. Wills,
J. Org. Chem., 2005, 70, 8079.
[3]. T. Saito, Y. Nishimoto, M. Yasuda and A. Baba, J. Org. Chem., 2006, 71, 8516.
[4]. F. Zhou and C.-J. Li, Nat. Commun., 2014, 5, 4254.
[5]. H. L. Ngo and W. Lin, J. Org. Chem., 2005, 70, 1177.
[6]. B. Denegri and O. Kronja, J. Org. Chem., 2007, 72, 8427.
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S30
Table S1. X-ray crystal structure refinement data of the complexes 1-4.
Complex 1 Complex 2 Complex 3 Complex 4
Crystal system Triclinic Monoclinic Monoclinic Monoclinic
Space group P -1 P 21/c P 21/c C 2/c
a (Å) 8.201(6) 16.376(11) 13.3979(7) 29.1612(11)
b (Å) 9.946(7) 10.424(7) 10.3168(5) 12.5438(5)
c (Å) 21.325(15) 20.145(10) 19.7429(9) 16.5284(6)
(˚) 81.89(3) 90 90 90
γ (˚) 87.42(2) 90 90 90
β (˚) 84.71(2) 127.64(4) 101.468(2) 103.261(2)
V (Å3) 1714(2) 2723(3) 2674.45 5884.75
Z 1 2 4 8
Temperature /K 150(2) 150(2) 150(2) 296(2)
λ (Å) (Mo-Kα) 0.71073 0.71073 0.71073 0.71073
Crystal size (mm) 0.4x0.2x0.1 0.1x0.1x0.1 0.2x0.15x0.1 0.2x0.15x0.1
F(000) 846 1356 1312 2752
Theta range for data
collection
3.0-27.4 3.14-26.35 2.24-28.22 3.00-26.25
Data/restraints/parameters 7351/0/ 354 5531/0/281 13667/0/799 15656/0/ 1025
GOF on F2 1.210 1.226 1.050 0.999
R1 [I > 2σ(I)] 0.0785 0.1139 0.0352 0.0577
wR2 [I > 2σ(I)] 0.2043 0.2066 0.0876 0.1840
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S31
Table S2. Selected bond lengths (Å) and angles (deg) of the complexes 1-4.
SI.No. Bond Lengths (Å) Bond Angles (deg)
Complex 1 C4-Ru1 2.074(7) C4-Ru-Cl3 89.0(2)
Cl2-Ru1 2.457(2) C4-Ru1-Cl2 89.44(19)
Cl3-Ru1 2.470(2) C4-Ru1-Cl3 89.0(2)
Ru1-CAr 1.719(2)
Complex 2 C1-Ru1 2.056(11) C1-Ru1-Cl1 90.0(3)
Cl1-Ru1 2.452(3) C1-Ru1-Cl2 89.70(3)
Cl2-Ru1 2.441(2) Cl2-Ru1-Cl1 83.49(9)
Ru1-CAr 1.693(2)
Complex 3 C1-Ru1 2.017(3) Cl1-Ru1-C1 84.11(7)
N3-Ru1 2.095(2) N3-Ru1-C1 76.65(11)
Cl1-Ru1 2.405(7) Cl1-Ru1-N3 84.14(7)
Ru1-CAr 1.714(3)
Complex 4 C12-Ru1 2.025(5) Cl1-Ru1-C12 84.84(14)
N4-Ru1 2.106(4) N4-Ru1-C12 76.04(18)
Cl1-Ru1 2.414(13) Cl1-Ru1-N4 88.76(12)
Ru1-CAr 1.740(2)
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S32
Table S3. Comparative efficiency of transfer hydrogenation of acetophenone in the presence of various catalysts.a
Entry Substrate Catalyst Conversion (%)
1
Complexes 1-2 90-100
2 ” Complexes 3-6 100
3 ” Ligands L1-L5 No reaction
4 ” [Ru(p-Cymene)Cl2]2 ~47
5 ” Hoveyda-Grubbs’ 2nd ~60 a Reaction conditions: acetophenone (0.1 mmol), catalysts entries 1, 3, 4 and 5 (2 mol%), catalyst entry 2 (0.5 mol%), NaOH (0.1 mmol), 2-propanol (2 mL), temperature (80 ± 2 °C) and reaction time, 1-5 h.
Table S4. Optimized energy levels of intermediates and molecules involved in the mechanism. a
Intermediate/Molecules Energy (a.u.)
(A) -1420.66
(B) -1227.47
(D) -1612.37
Acetone -193.13
Isopropanol -194.33
Acetophenone -384.84
1-Phenylethanol -386.04
aAverage of three independent calculations.
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S33
Scheme S1. Possible mechanism for transfer hydrogenation of acetophenone using complex 3 as
a representative example.