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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
5
(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
6
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
9
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.
10
Figure S9. UV-Visible spectra of VOTPPCl8 in CH2Cl2 (before catalysis) and in CH3CN (after catalytic reaction) at 298 K.