7KLV Journal: New J. Chem. Electronic Supplementary ...Mannar R. Maurya, Bithika Sarkar, Amit Kumar, Nádia Ribeiro, Aistè Miliute and J. Costa Pessoa 1H NMR spectroscopic data Fig

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Journal: New J. Chem. Manuscript ID: NJ-ART-03-2019-001486

Electronic Supplementary Information New thiosemicarbazide and dithiocarbazate based oxidovanadium(IV) and

dioxidovanadium(V) complexes. Reactivity and catalytic potential

Mannar R. Maurya, Bithika Sarkar, Amit Kumar, Nádia Ribeiro, Aistè Miliute and J. Costa Pessoa 1H NMR spectroscopic data

Fig. ESI-1 1H NMR spectra of H3dfmp-(smdt)2 (I), K[VVO2Hdfmp-(smdt)2] (4) recorded

in DMSO–d6. The (*) in figure indicates signal due to water in DMSO.

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 2019

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51V NMR spectroscopy data

Fig. ESI-2 51V NMR spectra of a solution of [VIVO{Hdfmp-(smdt)2}(MeOH)] (1) in MeOD (4

mM) a few minutes after addition of a solution of KOH in MeOD and after 2, 24, 48 and 72 h.

K[VVO2{Hdfmp(smdt)2}] – ~0 h

K[VVO2{Hdfmp(smdt)2}] – 2 h




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-1000-950-900-850-800-750-700-650-600-550-500-450-400-350-300-250-200-150-100-500f1 (ppm)

Fig. ESI-3 51V NMR spectra of K[VVO2{Hdfmp-(smdt)2}] (4) in MeOD (4 mM) and upon

additions of and aqueous solution of H2O2 (294 mM). The H2O2:4 molar ratios are specified in

each spectrum).

H2O2 / K[VVO2{Hdfmp(smdt)2}] - 0

H2O2 / K[VVO2{Hdfmp(smdt)2}] – 0.29







H2O2 / K[VVO2{Hdfmp(smdt)2}] – 28.97 – after 24 h

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Fig. ESI-4. 51V NMR spectra of Cs[VVO2{Hdfmp-(smdt)2}] (7) in MeOD (0.004 M) and upon

additions of and aqueous solution of H2O2 (294 mM). The H2O2:7 molar ratios are specified in

each spectrum).

H2O2 / Cs[VVO2{Hdfmp(smdt)2}] - 0

H2O2 / Cs[VVO2{Hdfmp(smdt)2}] – 0.29







H2O2 / Cs[VVO2{Hdfmp(smdt)2}] – 28.97 – after 24 h

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Addition of t-BuOOH instead of H2O2 to Cs[VVO2{Hdfmp-(smdt)2}] (7)

Fig. ESI-5A 51V NMR spectra of Cs[VVO2{Hdfmp-(smdt)2}] (7) (3 mM) in 10%

CD3OD:CH3OH with addition of t-butylhydroperoxide (250 mM), obtaining final ratios t-

BuOOH:7 of 0, 0.3, 0.7, 1, 2, 3, 5 and 10.

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Fig. ESI-5B 51V NMR spectra of Cs[VVO2{Hdfmp-(smdt)2}] (7) (3 mM) in 10%

CD3OD/ CH3OH with additions of HCl (250 mM), obtaining final ratios HCl : 7 of 0, 0.3,

0.7, 1, 2, 3, 5 and 10.

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UV-Vis absorption data

Fig. ESI-6 Spectral changes observed during titration of 25 mL of a 6.510–4 M solution in

DMSO of [VIVO{Hdfmp-(tsc)2(CH3OH)}] (3) with H2O2. The absorption spectra were

recorded with time upon stepwise additions of three drops portions of H2O2 (2.5×10–2 M in

DMSO). The inset shows expanded spectral region (730-820 nm), the spectra were recorded

upon stepwise additions of one drop portions of H2O2 solution (4.3×10–2 M in DMSO) to 25

mL of a 6.810–3 M solution of 3 in DMSO.

Fig. ESI-7 Titration of 25 mL of a 3.210–4 M solution in MeOH of Cs[VVO2{Hdfmp-

(sbdt)2}] (8). The absorption spectra were recorded upon stepwise additions of one drop

portions of H2O2 solution (1.6×10–2 M in DMSO).

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Fig. ESI-8 Titration of 25 mL of a methanolic solution of Cs[VVO2{Hdfmp-(tsc)2}] (9)

(6.310–4 M). The spectra were recorded upon stepwise additions of one drop portions of a

H2O2 solution (2.8×10–2 M).

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Thermal analysis data

Table ESI-1 Details of thermogravimetric analysis of complexes.

Compounds Temp. [oC] Observed a Calculated a Expected moiety/Residue

[VIVO{Hdfmp-(smdt)2}(CH3OH)] (1) 108

491

6.9 (m loss)

19.9

7.0 (m loss)

19.4

CH3OH

V2O5

[VIVO{Hdfmp-(sbdt)2}(CH3OH)] (2) 107

495

5.5 (m loss)

15.3

5.1 (m loss)

14.6

CH3OH

V2O5

[VIVO{Hdfmp-(tsc)2}(CH3OH)] (3) 108

475

8.4 (m loss)

23.1

7.8 (m loss)

22.3

CH3OH

V2O5

K[VVO2{Hdfmp-(smdt)2] (4) 584 27.5 27.9 KVO3

K[VVO2{Hdfmp-(sbdt)2] (5) 590 22.1 21.4 KVO3

K[VVO2{Hdfmp-(tsc)2] (6) 600 32.7 32.1 KVO3

Cs[VVO2{Hdfmp-(smdt)2] (7) 570 40.4 39.6 CsVO3

Cs[VVO2{Hdfmp-(sbdt)2] (8) 600 32.2 31.4 CsVO3

Cs[ [VVO2{Hdfmp-(tsc)2] (9) 578 54.8 53.9 CsVO3

a Mass losses are specified as ‘m loss’. The remaining numbers are the weight (in mg) of the

final residues.

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Table ESI-2 IR spectral data [cm–1] of the ligands and complexes.

Compounds N-H) C=S) C=N) C=N) N-N) C-S) V=O)

I

II 3085 1030 1609 _ 974 _ _

III 2980 1038 1611 _ 970 _ _

1 3056 1030 1605 1557 1052 670 991

2 3023 1032 1617 1560 1073 677 998

3 2996 1034 1615 1557 1070 689 996

4 2991 1038 1614 1560 1080 667 921, 895

5 3030 1043 1613 1554 1095 669 911, 893

6 2945 1037 1615 1558 1090 670 909, 891

7 3050 1038 1614 1559 1065 679 913, 896

8 3034 1034 1611 1556 1068 700 913, 897

9 2923 1030 1612 1560 1072 695 908, 890

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Table ESI-3 UV-visible spectral data of ligands and vanadium complexes either in methanol or DMSO. Compounds Solvent λmax /nm (/ M–1cm–1)

H3dfmp-(smdt)2 (I) DMSO 329 (3.3×104), 345 (3.7×104), 365 (3.2×104), 401 (2.6×104)

[VIVO{Hdfmp-(smdt)2}(CH3OH)] (1) DMSO 312 (3.08×103), 337 (2.7× 103), 419 (1.78× 103)

K[VVO2{Hdfmp-(smdt)2}] (4) MeOH 253 (3. ×104), 310 (5.1×104), 335 (3.7×104), 427 (4.3×103)

Cs[VVO2{Hdfmp-(smdt)2}] (7) MeOH 206 (1.9×104), 311 (2.7×104), 333 (3.5×104), 417 (1.1×103)

H3dfmp-(sbdt)2 (II) DMSO 329 (4×104), 345 (4.5×104), 367 (4×104), 405 (3.2×104)

[VIVO{Hdfmp-(sbdt)2}(CH3OH)] (2) DMSO 258 (3.6×104), 320 (2.4× 104), 369 (1.6×104), 407 (1.38×104)

K[VVO2{Hdfmp-(sbdt)2}] (5) MeOH 247 (5.26×104), 318 (5.26×104), 363 (5.26×104), 413 (5.26×104)

Cs[VVO2{Hdfmp-(sbdt)2}] (8) MeOH 256 (2.27×104), 301 (3.37×104), 354 (1.38×104), 411(×104)

H3dfmp-(tsc)2 (III) DMSO 315 (4.9×104), 328 (4.2×104), 369 (2.7×104), 387 (3.37×104)

[VIVO{Hdfmp-(tsc)2}(CH3OH)] (3) DMSO 247 (6.2×104), 316 (4.5× 104), 369 (1.9×103), 418 (3.3×103)

K[VVO2{Hdfmp-(tsc)2}] (6) MeOH 203 (2.23×104), 305 (3.36×104), 360 (5.45×104), 430 (5.39×103)

Cs[VVO2{Hdfmp-(tsc)2}] (9) MeOH 252 (4.67×104), 317 (3.34×104), 364 (2.36×104), 412 (1.26×103)

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Table ESI-4 13C NMR spectral data (δ in ppm) of ligand precursors and VVO2-

complexes obtained in DMSO-d6.

Compound C1 C2 C3/C4 C5/C6 C7 C8/C9 C10/C11 C12/C13

I 20.3 129.7 129.3 119.9 155.0 145.5 197.9 17.2

4 20.4 128.7 131.4

132.7

121.5

122.5

162.2 158.3,

142.2

174.5,

197.1

17.5

IIa 20.4 129.6 131.7 120.1 155.0 145.2 197.8 -

5a 20.4 130.1,

135.3

132.6 122.7 163.2 158.6,

144.3

179.3,

197.3

-

III 20.3 129.3 130.9 121.2 153.2 141.8 178.2 -

6 20.3 131.3,

134.6

125.4

128.7

123.1 161.3 150.5,

142.6

174.6,

196.7

-

a Singals due to benzene ring of benzyl group, II: 127.7, 128.9, 129.4, 137.0 and 5: 127.9, 128.4, 129.8, 139.2.

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Oxidation of benzyl alcohol

Table ESI-5 Oxidation of benzyl alcohol (1.08 g, 0.010 mol) obtained at different

reaction conditions using Cs[VVO2{Hdfmp-(smdt)2}] (7) as catalyst precursor.

Entry No.

Benzyl alcohol [g (mol)]

H2O2

[g (mol)] Catalyst

[g] Solvent

(CH3CN) [mL]

Temperature [ºC]

Conv. [%]

1 1.08 (0.010) 2.27 (0.020) 0.002 5 80 60

2 1.08 (0.010) 2.27 (0.020) 0.003 5 80 72

3 1.08 (0.010) 2.27 (0.020) 0.004 5 80 73

4 1.08 (0.010) 1.13 (0.010) 0.003 5 80 56

5 1.08 (0.010) 3.34 (0.030) 0.003 5 80 76

6 1.08 (0.010) 2.27 (0.020) 0.003 7 80 74

7 1.08 (0.010) 2.27 (0.020) 0.003 10 80 75

8 1.08 (0.010) 2.27 (0.020) 0.003 5 70 62

9 1.08 (0.010) 2.27 (0.020) 0.003 5 90 76

Fig. ESI-9 Effect of no addition of catalyst in the oxidation of benzyl alcohol. Reaction

conditions: Benzyl alcohol (1.08 g, 0.010 mol), catalyst (0.003 g), 30% H2O2 (2.27 g, 0.020

mol) and acetonitrile (5 mL).

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Fig. ESI-10 Comparison of the catalytic performance of different VVO2-catalysts for the

oxidation of benzyl alcohol.

Oxidation of ethylbenzene

Table ESI-6 Oxidation of ethyl benzene (1.06 g, 0.010 mol) obtained at different reaction

conditions using Cs[VVO2{Hdfmp-(smdt)2}] (7) as catalyst.

Entry No.

Ethyl benzene [g (mol)]

H2O2 [g (mol)]

Catalyst [g] Solvent (CH3CN)

[mL]

Temperature[ºC]

Conv. [%]

1 1.06 (0.010) 2.27 (0.020) 0.001 5 80 45

2 1.06 (0.010) 2.27 (0.020) 0.002 5 80 51

3 1.06 (0.010) 2.27 (0.020) 0.003 5 80 66

4 1.06 (0.010) 1.13 (0.010) 0.003 5 80 45

5 1.06 (0.010) 3.34 (0.030) 0.003 5 80 65

6 1.06 (0.010) 2.27 (0.020) 0.003 10 80 66

7 1.06 (0.010) 2.27 (0.020) 0.003 15 80 68

8 1.06 (0.010) 2.27 (0.020) 0.003 5 70 50

9 1.06 (0.010) 2.27 (0.020) 0.003 5 90 71

Documents

7KLV Journal: New J. Chem. Electronic Supplementary ...Mannar R. Maurya, Bithika Sarkar, Amit Kumar, Nádia Ribeiro, Aistè Miliute and J. Costa Pessoa 1H NMR spectroscopic data Fig