Thieme

Supporting Information for DOI: 10.1055/s-0037-1610177

© Georg Thieme Verlag KG Stuttgart · New York 2018

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Supporting Information

Synthesis of water soluble ruthenium complex and its catalytic activity for

acceptorless alcohol dehydrogenation in aqueous medium

Anita Bhatia, Senthilkumar Muthaiah*

Department of Chemistry, National Institute of Technology, Kurukshetra-136119,

Haryana, India

E-mail: msenthil@nitkkr.ac.in

Table of Contents

1 Experimental Section S2-S3

2 1H, 13C{1H} and 31P{1H}-NMR Spectra of the ruthenium complex 2 S4-S5

3 1H-NMR Spectra of the oxidized products S5-S12

4 References S12

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Experimental Section

General Information

All procedures and manipulations were carried out under purified nitrogen environment using a standard Schlenk apparatus. All the apparatus were oven dried prior to use. Airless procedure was followed for all syntheses irrespective of air stability of final compounds. All the solvents were used after drying and degassing process. Other chemicals were purchased from commercial suppliers and used as received without further purification. 1,3,5-triaza-7-phosphadamantane (PTA) was synthesized as per method reported in literature.1 Ligand 1 was prepared by using the reported procedure in literature.2 Nuclear Magnetic Resonance spectra were recorded using Bruker Advance II 400 MHz NMR spectrometer. Chemical shifts were reported in ppm. GC analysis for calculation of yields of the products was carried out with Trace 1110 GC system from Thermofischer scientific, equipped with a DB-5MS column and FID detector.

Synthesis of [RuCl2(PPh3)2(2-PyCH2PTA)].Br (2)

In an oven dried Schlenk flask [2-PyCH2PTA].Br (1) (0.329g, 1 mmol) was added to a solution of RuCl2(PPh3)3 (0.881g,1 mmol) in toluene (ca. 50 mL). After refluxing the resulting mixture for around 12 h, the reaction mixture was cooled down and filtered. The brown residue obtained was washed with hexane and dried under vacuo to get the analytically pure product. Yield: 0.860 g (90%); 1H NMR (CDCl3, 25 oC): δ(ppm) 2.47 (d, J = 16 Hz, 2H, PCHAHBN), 2.88 (d, J = 16 Hz, 2H, PCHAHBN)), 2.98 (d, J = 12 Hz 2H, PCH2N+), 3.11 (s, 1H, NCHAHBN), 3.55 (s, 1H, NCHAHBN), 4.31 (s, 2H, N+CH2CPy), 5.09 (d, J = 12 Hz, 2H, N+CHAHBN), 5.24 (d, J = 12 Hz, 2H, N+CHAHBN), 7.16-7.21 (m, 30H, PPh3, 1H, HPy), 7.67 (t, J = 8 Hz, 1H, HPy), 8.51 (d, J = Hz 2H, HPy); 13C{1H} NMR (DMSO, 25oC): δ(ppm) 49.88 (d, JPC = 52 Hz, PCH2N); 54.09 (d, JPC = 52 Hz, PCH2N+); 68.42 (s, pyCH2N+); 72.03 (s, NCH2N); 73.36 (s, NCH2N+); 128.68 (s, Cpy); 131.41 (s, Cpy); 133.17 (d, JPC=36 Hz, CPh); 136.47 (s, Cpy); 141.11 (s, CPh); 144.99 (s, Cpy); 151.83 (s, Cpy).31P{1H} NMR (DMSO-d6): δ(ppm) -26.68 (t, JPP =36 Hz, Ru-PTA), 29.22 (d, JPP =36 Hz, Ru-PPh3). Elemental analysis: anal cal. for C48H48Cl2BrN4P3Ru: C 56.21, H 4.72 and N 5.46; found C 56.17, H 4.70 and N 5.41. ESI-MS (+ve) (m/z) = 945.31[M]+. General procedure for dehydrogenation of alcohols Ruthenium complex 2 (5 mol%), KOH (15 mol%), alcohol (5 mmol) and H2O (1.0 mL) were placed in Schlenk tube. The reaction mixture was stirred under reflux for 48 h. After completion of the reaction, the product was extracted with dichloromethane. Then all DCM were evaporated under vacuo, the product ketones and aldehydes were isolated from crude mixture by column chromatography using hexane/EtOAc as eluent. The formation of products was confirmed by comparing the 1H-NMR data with literature reports.

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1H NMR data of the Products:

Acetophenone (4a):1H NMR (400 MHz,CDCl3,): 2.58 (s, 3 H), 7.43–7.57 (m, 3H), 7.94-7.96 (m, 2 H).3

1-(4-methylphenyl)ethanone(4b): 1H NMR (400 MHz, CDCl3),: 2.41 (s, 3 H), 2.57 (s, 3 H), 7.24-7.26 (m, 2 H), 7.85-7.87 (m,2H).3

1-(4-Methoxyphenyl)ethanone (4c):1H NMR (400 MHz, CDCl3): 2.56 (s, 3 H), 3.87 (s, 3 H), 6.92–6.95(m, 2 H), 7.93–7.95 (m, 2 H).3

1-(4-Chlorophenyl)ethanone (4d):1H NMR(400 MHz, CDCl3): 2.59 (s, 3 H), 7.42 (d, 2H), 7.89 (d,2H).3

1-(4-Bromophenyl)ethanone (4e):1H NMR (400 MHz , CDCl3) δ 2.59 (s, 3 H, Me), 7.59−7.61 (m, 2 H, C6H4), 7.81-7.83 (m, 2 H, C6H4).3

1-(4-Nitrophenyl)ethanone (4f):1H NMR (400 MHz , CDCl3) δ 2.70 (s, 3 H, Me), 8.12−8.14 (m, 2 H, C6H4), 8.31-8.33 (m, 2 H C6H4).3

Cyclohexanone (4g):1H NMR (400 MHz , CDCl3) δ 2.34 (t, 2 H ), δ 1.85-1.88 (m, 2 H ), δ 1.73-1.74 (m, 1 H ).4

5-hexen-2-one (4h):1H NMR (400 MHz , CDCl3) d 2.15 (s, 3H), 2.31-2.35 (m, 2H), 2.52-2.56 (m, 2H), 4.96-5.05 (m, 2H), 5.76-5.86 (m, 1H).5

3-methyl-2-ketone (4i):1H NMR (CDCl3) δ 1.11 (d, 6H ), 2.15 (s, 3H), 2.56-2.66 (m, 1H).4

Benzophenone (4j):1H NMR (CDCl3) δ 7.46−7.50 (m, 4 H, Ar), 7.57-7.61 (m, 2 H, Ar), 7.79-7.82 (m, 4 H, Ar).7

Benzaldehyde (4k): 1H NMR (CDCl3) δ 7.46-7.88(5H, Ar ), 10(s,1H).6

4-Methoxy Benzaldehyde (4l): 1H NMR (CDCl3) δ 3.81 (s, 3H), 6.94 (d,2H), 7.75 (d, 2H), 9.82(s, 1H).6

1-(2-methoxyphenyl)ethanone(4m): 1H NMR (400 MHz, CDCl3,25 ºC), 2.54 (s, 3 H), 3.83 (s, 3 H), 6.98-7.05(m, 2 H), 7.39-7.43 (m,1H), 7.72-7.74(dd, 1H).3

1-(3-Bromophenyl)ethanone (4n):1H NMR (400 MHz, CDCl3) δ 2.54 (s, 3 H, Me), 7.27(t, 1H),7.61 (d, 1H), 7.75 (d, 1H), 8.01(s,1H).7

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Figure 1 : 1H NMR data of compound 2 :

Figure 2 : 31P{1H} NMR data of compound 2:

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Figure 3 : 13C{1H} NMR data of compound 2

Figure 4 : 1H NMR data of 4a

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Figure 5 : 1H NMR data of 4b

Figure 6 : 1H NMR data of 4c

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Figure 7 : 1H NMR data of 4d

Figure 8 : 1H NMR data of 4e

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Figure 9 : 1H NMR data of 4f

Figure 10 : 1H NMR data of 4g

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Figure 11 : 1H NMR data of 4h

Figure 12 : 1H NMR data of 4i

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Figure 13 : 1H NMR data of 4j

Figure 14 : 1H NMR data of 4k

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Figure 15 : 1H NMR data of 4l

Figure 16 : 1H NMR data of 4m

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Figure 17 : 1H NMR data of 4n

References [1] Daigle, D. J. in: Darensbourg (Ed.), Inorg. Synth. 1998, 32, 40.

[2] Krogstad, D.A.; Ellis, G.S.; Gunderson, A.K.; Hammrich, A.J.; Rudolf, J.W.; Halfen, J.A. Polyhedron 2007, 26,

4093-4100. [3] Hou, S.; Yang, H.; Chang, B.; Zhai, H.; Li, Y. Chem. Commun., 2017,53, 6926-6929 [4] Yang, J.-J.; Li, C.-C.; Yang, Y.-F.; Wang, C.-Y.; Lin, C.-H.; Lee, J.-T. RSC Adv.2016, 6(68), 63472-63476;

[5] Smit, B.M.; Pavlovic, R.Z. Tetrahedron, 2015, 71, 1101-1108;

[6] Zhang, G.; Wang, Y.; Wen X.; Ding, C.; Li, Y. Chem. Commun., 2012, 48, 2979-2981. [7 ] Liu, X.; Lin, L.; Ye, X.; Tan, C.-H.; Jiang, Z. Asian J. Org. Chem. 2017, 6, 422-425. [8] Murahashi, S.-I.; Naota, T.; Ito, K.; Maeda, Y.; Taki, H. J. Org. Chem. 1987,52, 4319-4327.

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