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Electron Deficient Nonplanar β-Octachlorovanadylporphyrin as Highly Efficient and Selective Epoxidation Catalyst for Olefins

Ravi Kumar, Nikita Chaudhary, Muniappan Sankar* and Mannar R. Maurya*

Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee – 247667, India

Table of Contents

Page No

Figure S1. FT-IR spectra of (a) H2TPPCl8 and (b) VOTPPCl8 using KBr pellets. 2

Figure S2. MALDI-TOF mass spectra of VOTPPCl8 using HABA matrix. Insets show the

molecular ion peaks obtained from experiment and simulation.

3

Table S1. Selected bond lengths (A) and bond angles (°) for the B3LYP/6-311G(d,p) optimised

geometry of VOTPPCl8 in CH3CN. The values if the given figure represent the deviation of

atoms from the porphyrin mean plane formed by 24 atoms core.

4

Figure S3. B3LYP/LANDLD2Z optimized geometry showing (a) top and (b) side view of

H2TPPCl8 in CH3CN. In side view, β-chloro and meso-phenyl groups are not shown for clarity.

5

Table S2. Selected bond lengths (Å) and bond angles (°) for the B3LYP/6-311G(d,p) optimised

geometry of H2TPPCl8 in CH3CN. The values if the given figure represent the deviation of

atoms from the porphyrin mean plane formed by 24 atoms core.

5

Figure S4. DPV of VOTPPCl8 in CH2Cl2 indicating one electron redox processes. 6

Figure S5. CV and DPV of VOTPPCl8 in CH2Cl2 containing 0.1 M TBAPF6 at 298 K. 7

Figure S6. Thermogram (TG), Differential thermal analysis (DTA) and Differential thermogram

(DTG) of VOTPPCl8 at the heating rate of 10 °C /minute scanned from 25 °C to 1000 °C.

8

Figure S7. MALDI-TOF mass spectra of VOTPPCl8 in presence of hydrogen peroxide and

sodium bicarbonate using HABA matrix.

9

Figure S8. MALDI-TOF mass spectra of the reaction mixture after addition of the cyclohexene

to oxido- peroxidovanadium(V) intermediate using HABA matrix.

9

Figure S9. UV-Visible spectra of VOTPPCl8 in CH2Cl2 (before catalysis) and in CH3CN (after

catalytic reaction) at 298 K.

10

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2015

2

(a)

νN-H 3328 cm-1

(b)

νV=O 1003 cm-1

Figure S1. FT-IR spectra of (a) H2TPPCl8 and (b) VOTPPCl8 using KBr pellets.

3

Figure S2. MALDI-TOF mass spectra of VOTPPCl8 using HABA matrix. Insets show the molecular ion peaks obtained from experiment and simulation.

4

Table S1. Selected bond lengths (Å) and bond angles (°) for the B3LYP/6-311G(d,p) optimised geometry of VOTPPCl8 in CH3CN. The values if the given figure represent the deviation of atoms from the porphyrin mean plane formed by 24 atoms core.

N1

N2

N3

N4

-1.158-1.158

-0.4150.008

0.4311.098

1.0980.431

0.008-0.415

-1.158 -1.158

-0.4150.008

0.4311.098

1.0980.431

0.008-0.415

0.141 0.141

-0.071

-0.071

V0.535

N

N

N

N

C

Ca Ca

CaCa

C C

C

CC

C C

V

Cm

Cm Cm

Cm

C

C C

C

aDeviation of β-pyrrole carbons from porphyrin mean plane formed by 24-atom corebDeviation of 24 atoms from the porphyrin mean plane

cdeviation of metal atom (VIV) from the porphyrin mean plane

Bond Length (Å) Bond Angle (°)V-N 2.065 M-N-Cα 123.00V-O 1.602 N-M-N 153.06N-Cα 1.402 N-Cα-Cm 123.80Cα-Cβ 1.452 N-Cα-Cβ 107.82Cβ-Cβ 1.375 Cβ- Cα-Cm 128.16Cα-Cm 1.413 Cα-Cβ-Cβ 107.89

ΔCβ (Å)a 1.128 Cα-N-Cα 107.90Δ24 (Å)b 0.535

ΔMetal (Å)c 0.515

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(a) (b)

Figure S3. B3LYP/LANDLD2Z optimized geometry showing (a) top and (b) side view of H2TPPCl8 in CH3CN. In side view, β-chloro and meso-phenyl groups are not shown for clarity.

Table S2. Selected bond lengths (Å) and bond angles (°) for the B3LYP/6-311G(d,p) optimised geometry of H2TPPCl8 in CH3CN. The values if the given figure represent the deviation of atoms from the porphyrin mean plane formed by 24 atoms core.

N1

N2

N3

N4

-1.202-1.202

-0.4080.008

0.4151.168

1.1680.415

0.008-0.408

-1.202 -1.202

-0.4080.008

0.4151.168

1.1680.415

0.008-0.408

0.056 0.056

-0.017

-0.017

HN

N

NH

N

C

Ca Ca

CaCa

C C

C

CC

C C

Cm

Cm Cm

Cm

C

C C

C

aDeviation of β-pyrrole carbons from porphyrin mean plane formed by 24-atom core.bDeviation of 24 atoms from the porphyrin mean plane.

Bond Length (Å) Bond Angle (°)N-Cα 1.389 N-Cα-Cm 124.10Cα-Cβ 1.457 N-Cα-Cβ 106.74Cβ-Cβ 1.377 Cβ- Cα-Cm 129.03Cα-Cm 1.422 Cα-Cβ-Cβ 108.02

ΔCβ (Å)a 1.185 Cα-N-Cα 110.15Δ24 (Å)b 0.674

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Figure S4. DPV of VOTPPCl8 in CH2Cl2 indicating one electron redox processes.

7

(a)

(b)

Figure S5. CV and DPV of VOTPPCl8 in CH2Cl2 containing 0.1 M TBAPF6 at 298 K.

8

Figure S6. Thermogram (TG), Differential thermal analysis (DTA) and Differential thermogram (DTG) of VOTPPCl8 at the heating rate of 10 °C /minute scanned from 25 °C to 1000 °C.

Temp Cel1000900800700600500400300200100

DTA

uV

600.0

400.0

200.0

0.0

-200.0

-400.0

-600.0

TG %

250.0

200.0

150.0

100.0

50.0

0.0

DTG

mg/

min

2.00

1.00

0.00

-1.00

-2.00

-3.00

-4.00

-5.00

-6.00

-7.00

25.7 Cel99.99 %

99.7 Cel98.55 %

200 Cel96.38 %

300 Cel92.27 %

1014 Cel6.602 %

405 Cel1.20 mg/min

460 Cel0.57 mg/min

485 Cel8.0 %

472 Cel212.4 uV

442 Cel212.3 uV

400 Cel84.3 %

-14.4 J/mg

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956 [M+H]+ [VOTPPCl8

Calcd. 989.25 [H(OxidoperoxidoVanadium(V)TPPCl8

Figure S7. MALDI-TOF mass spectra of VOTPPCl8 in presence of hydrogen peroxide and sodium bicarbonate using HABA matrix.

Calcd. 955

Figure S8. MALDI-TOF mass spectra of the reaction mixture after addition of the cyclohexene to oxido- peroxidovanadium(V) intermediate using HABA matrix.

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Figure S9. UV-Visible spectra of VOTPPCl8 in CH2Cl2 (before catalysis) and in CH3CN (after catalytic reaction) at 298 K.