Electronic Supplementary Information

Cu(II), Co(II) and Ni(II) complexes installed on functionalized silica

surface for hydrogen peroxide assisted cyclohexane oxidation

R. Antony, S. Theodore David Manickam* and S. Balakumar

Table of Contents

Table S1. Physico-chemical data of DIPA, [Cu(DIPA)2], [Co(DIPA)2] and [Ni(DIPA)2]

Figure S1. IR spectra of DIPA and [Co(DIPA)2]

Figure S2. Expanded version (450-800 nm) of UV-Vis. spectra of DIPA and [M(DIPA)2]

Figure S3. DR UV-Vis. spectra of silica, FSG, [Cu(DIPA)2FSG] and [Co(DIPA)2FSG]

Figure S4. 1H NMR spectrum of DIPA

Figure S5. SEM images of silica, and FSG and FE-SEM image of [Co(DIPA)2FSG] (from

left to right)

Figure S6. UV-Vis. spectrum of [Cu(DIPA)2FSG] in presence of nitric acid, H2O2 and

acetonitrile

Figure S7. UV-Vis. spectrum of [Co(DIPA)2FSG] in presence of nitric acid, H2O2 and

acetonitrile

Figure S8. UV-Vis. spectrum of [Ni(DIPA)2FSG] in presence of nitric acid, H2O2 and

acetonitrile

Figure S9. Solid state CP MAS 29Si NMR spectrum of FSG

Scheme S1. Mechanism of cyclohexane oxidation catalyzed by synthesized catalysts

Table S2. Conversion and selectivity % of cyclohexane oxidation reaction at various reaction

times with different catalysts

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Table S1: Physico-chemical data of DIPA, [Cu(DIPA)2], [Co(DIPA)2] and [Ni(DIPA)2]

Compound (Formula)

Elemental analysis (%)Calculated (Found)

Molar conductivity

Magnetic susceptibility

C H N

DIPA (C15H17N3O4)59.40(59.15)

5.65(5.48)

13.85(13.74) 5 0

[Cu(DIPA)2] (C30H32N6O8Cu) 53.93(52.99)

4.83(4.57)

12.58(12.54) 11 1.70

[Co(DIPA)2] (C30H32N6O8Co) 54.3153.55

4.864.72

12.6612.43 9 1.72

[Ni(DIPA)2] (C30H32N6O8Ni) 54.3353.28

4.864.73

12.6712.50 13 0

Figure S1. IR spectra of DIPA and [Co(DIPA)2]

Figure S2. Expanded version (450-800 nm) of UV-Vis. spectra of DIPA and [M(DIPA)2]

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Figure S3. DR UV-Vis. spectra of silica, FSG, [Cu(DIPA)2FSG] and [Co(DIPA)2FSG]

Figure S4. 1H NMR spectrum of DIPA

Figure S5 (a). SEM image of silica

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Figure S5 (b). SEM images of silica, and FSG and FE-SEM image of [Co(DIPA)2FSG]

Figure S5 (c). SEM image of FE-SEM image of [Co(DIPA)2FSG]

Figure S6. UV-Vis. spectrum of [Cu(DIPA)2FSG] in presence of HNO3, H2O2 and CH3CN

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Figure S7. UV-Vis. spectrum of [Co(DIPA)2FSG] in presence of HNO3, H2O2 and CH3CN

Figure S8. UV-Vis. spectrum of [Cu(DIPA)2FSG] in presence of HNO3, H2O2 and CH3CN

Figure S9. Solid state CP MAS 29Si NMR spectrum of FSG

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Scheme S1. Mechanism of cyclohexane oxidation catalyzed by synthesized catalysts

Table S2: Conversion and selectivity % of cyclohexane oxidation reaction at various reaction times with different catalysts

Catalyst Time (h) Conversion (%) Selectivity (%)Cyclohexanol Cyclohexanone

[Cu(DIPA)2] 2 14 88 124 25 71 296 33 57 438 41 39 6110 43 31 69

[Co(DIPA)2] 2 9 90 104 18 79 216 30 67 338 35 55 4510 37 51 49

[Ni(DIPA)2] 2 7 93 74 14 84 166 27 75 258 31 65 3510 32 63 37

[Cu(DIPA)2FSG] 2 45 82 184 67 70 306 69 55 458 70 34 6610 71 28 72

[Co(DIPA)2FSG] 2 32 85 154 45 74 266 51 67 338 53 52 4810 55 44 56

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[Ni(DIPA)2FSG] 2 25 89 114 40 79 216 42 68 328 44 59 4110 45 55 45

CuCl2.2H2O 10 18 41 59CoCl2.6H2O 10 <5 37 63NiCl2.6H2O 10 <5 44 56Conditions: 5 mmol cyclohexane, 10 mmol 30% H2O2, 50 mg (if the catalyst is supported) or else 25 µmol catalyst, 10 ml CH3CN and 70 oC

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