Supplementary Data
Mononuclear, Helical Binuclear Palladium and Lithium Complexes Bearing a
New Pyrrole-based NNN-Pincer Ligand: Fluxional Property
Debasish Ghorai, Shanish Kumar and Ganesan Mani*
Department of Chemistry, Indian Institute of Technology, Kharagpur, India 721 302
Fax: +91 3222 282252, E-mail: gmani@chem.iitkgp.ernet.in
Table of contents
I.
NMR and IR spectra
II.
X-ray Crystallography
S2
S16
S1
I. NMR and IR spectra
N
N
N
H
Figure S1. 1H NMR spectrum of 2,5-bis(dimethylaminomethyl)pyrrole, 1 in CDCl3.
N
N
N
H
N
N
Figure S2. 1H NMR spectrum of 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2 in CDCl3.
S2
Figure S3. 1H NMR spectrum of 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2 in toluene-d8.
N
N
N
H
N
N
Figure S4. 13C{1H} NMR spectrum of 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2 in CDCl3.
S3
67.0
65
467.36
60
621.03
917.43
55
697.01
50
1210.95
45
N
N
3198.44
%T
N
H
N
N
40
1271.15
1030.21
3127.07
35
1548.85
1377.85
790.95
30
1459.74
2854.98
25
2921.19
20.0
4000.0
3600
3200
2800
2400
2000
1800
cm-1
1600
1400
1200
1000
800
600
450.0
Figure S5. IR spectrum of 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2 recorded as a KBr disc.
N
N
N
N
N
Pd
O
O
Figure S6. 1H NMR spectrum of [Pd(OAc){C4H2N-2,5-(CH2Me2pz)2-N,N,N}], 3 in CDCl3.
S4
N
N
N
N
N
Pd
O
O
Figure S7. 13C{1H} NMR spectrum of [Pd(OAc){C4H2N-2,5-(CH2Me2pz)2-N,N,N}], 3 in CDCl3.
73.6
72
70
1037.11
68
737.10
623.08
2928.94
3121.27
66
812.30
1266.72
683.56
1651.25
64
1467.83
2363.92
62
%T
1338.01
3441.64
3524.18
60
58
N
N
N
Pd
56
O
1423.91
N
N
O
1587.91
1389.77
54
52
50.0
3700.0
3200
2800
2400
2000
1800
1600
cm-1
1400
1200
1000
800
600
450.0
Figure S8. IR spectrum of [Pd(OAc){C4H2N-2,5-(CH2Me2pz)2-N,N,N}], 3 recorded as a KBr disc.
S5
N
N
N
N
N
Li
Li
N
N
N
N
N
4
Figure S9. 1H NMR spectrum of [Li{-C4H2N-2,5-(CH2Me2pz)2-N,N,N}]2, 4 in toluene-d8.
N
N
N
N
N
Li
Li
N
N
N
N
N
4
Figure S10. 13C{1H} NMR spectrum of [Li{-C4H2N-2,5-(CH2Me2pz)2-N,N,N}]2, 4 in toluene-d8.
S6
68.7
65
60
55
50
45
477.93
40
35
651.88
920.75
3064.20
706.11
%T
30
25
1342.15
20
1499.09
812.58
15
1546.67
10
1263.13
738.40
1087.44
1030.42
5
2850.63
766.89
1383.60
2924.46
0
-2.0
3600.0
1459.00
3200
2800
2400
2000
1800
1600
cm-1
1400
1200
1000
800
600
450.0
Figure S11. IR spectrum of [Li{-C4H2N-2,5-(CH2Me2pz)2-N,N,N}]2, 4 recorded as a Nujol mull.
N
N
N
Pd
N
N
Cl
Figure S12. 1H NMR spectrum of [PdCl{C4H2N-2,5-(CH2Me2pz)2-N,N,N}] 5 in CDCl3.
S7
N
N
N
Pd
N
N
Cl
Figure S13. 13C{1H} NMR spectrum of [PdCl{C4H2N-2,5-(CH2Me2pz)2-N,N,N}] 5 in CDCl3.
N
N
N
Pd
N
N
Cl
Figure S14. IR spectrum of [PdCl{C4H2N-2,5-(CH2Me2pz)2-N,N,N}] 5 recorded as a Nujol mull.
S8
Cl
Pd
N
N
N
H
N
N
Pd Cl
Cl
Cl
N
H
N
N
N
N
Figure S15. 1H NMR spectrum of [Pd2Cl4{-C4H3N-2,5-(CH2Me2pz)2-N,N}2] 6 in CDCl3.
N
Cl
Pd
N
N
N
N
H
N
N
Pd Cl
Cl
Cl
H
N
N
N
Figure S16. 13C{1H} NMR spectrum [Pd2Cl4{-C4H3N-2,5-(CH2Me2pz)2-N,N}2] 6 in CDCl3.
S9
76.2
75
74
73
603.62
72
1718.69
684.24
2370.39
71
70
1654.33
69
68
67
1573.19
1032.61
1264.31
798.89
66
1420.34
%T 65
2855.91
64
N
63
62
61
Cl
Pd
N
N
H
N
N
Pd Cl
Cl
Cl
3262.69
N
60
N
59
N
H
N
N
58
57
2924.49
56
55.0
3600.0
3200
2800
2400
2000
1800
1600
cm-1
1400
1200
1000
800
600
450.0
Figure S17. IR spectrum of [Pd2Cl4{-C4H3N-2,5-(CH2Me2pz)2-N,N}2] 6 recorded as a KBr disc.
S10
Figure S18. Variable-temperature 1H NMR spectra (400 MHz) of complex 3 in CDCl3 (0.04 M)
showing a broad singlet for its diastereotopic methylene protons at 50 C due to the fast
interconversion between the two enantiomers on the NMR time scale. The coalescence
temperature Tc is the same as that observed for 0.02 M sample.
S11
Figure S19. 1H NMR spectrum (400 MHz) of complex 3 in DMSO-d6 showing a sharp singlet for
its diastereotopic methylene protons at room temperature (25°C), indicating DMSO is involved in
the interconversion process.
S12
Figure S20. Variable-temperature 1H-NMR spectra (400 MHz) of complex 5 in CDCl3 (0.024 M)
showing a broad singlet for its diastereotopic methylene protons at 60 C due to the fast
interconversion between the two enantiomers on the NMR time scale. The peak at 5.30 is due
CH2Cl2.
S13
Figure S21. Variable-temperature 1H-NMR spectra (400 MHz) of complex 5 in CDCl3 (0.04 M)
showing a broad singlet for its diastereotopic methylene protons at 60 C due to the fast
interconversion between the two enantiomers on the NMR time scale. The coalescence
temperature Tc is the same as that observed for 0.024 M sample.
S14
Figure S22. Variable-temperature 1H-NMR spectra (400 MHz) of complex 5 in DMSO-d6 (0.04
M), showing a broad singlet for its diastereotopic methylene protons at 50 C due to the fast
interconversion between the two enantiomers on the NMR time scale. DMSO is involved in the
interconversion process.
S15
II. X-ray Crystallography
Crystal structure of 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole, 2
The interesting feature of the structure of 2 is the trans or perpendicular orientation of the two
pyrazole rings to the mean plane formed by the pyrrole ring and the two methylene carbon atoms,
which minimizes the steric congestion between the pyrazole moieties.
(b)
(a)
Figure S23. Molecular structure of 2: (a) side view and (b) top view with 30% thermal ellipsoids.
The disordered oxygen atoms of the two water molecules are omitted. Dotted lines indicate
hydrogen bonds. Selected bond lengths (Å) and angles (): N1–N2 1.339(5), N2–C6 1.473(6), C6–
C7 1.490(6), N3–C7 1.354(5), C7-C8 1.359(6), C8-C9 1.415(7), C9-C10 1.360(6), N3–C10
1.365(6), C10–C11 1.463(6), N4–C11 1.466(5), N4–N5 1.372(6), N1–N2–C6 121.0(5), C4–N2–
N1 112.9(5), C7–N3–C10 111.7(4), C13–N4–N5 112.1(5), N5–N4–C11 117.9(5), N2–C6–C7
111.9(3), N3–C10–C11 122.7(6), C10–C11–N4 112.3(3).
S16
Table S1 Crystallographic data for compounds 2∙2H2O
2∙2H2O
Empirical formula
C16H25N5O2
Formula weight
319.41
Wavelength (Å)
0.71073
Temperature (K)
293(2)
Crystal system
Orthorhombic
Color and shape
Colorless, needle
Space group
Pca21
a/Å
25.795(7)
b/Å
4.4057(12)
c/Å
16.118(4)
α/degree
90.00
β/degree
90.00
γ/degree
90.00
Volume(Å3)
1831.7(9)
Z
4
Dcalcd , g cm-3
1.158
µ/mm-1
0.079
F(000)
688
Crystal size/mm
0.35×0.05×0.04
 range(degree)
1.58 to 25.00
Limiting indices
30<=h<=30
5<=k<=5
19<=l<=18
Total/ unique no. of reflns.
19760 / 3221
Rint
0. 1100
Data / restr./ params.
2
3221 / 1 / 215
GOF(F )
1.005
R1, wR2
0.0553, 0.1147
R1, wR2 (all data)
0.1565, 0.1627
peak and hole
0.102 and 0.104
–3
(e Å )
S17
Figure S24. Unit cell packing diagram for 2∙2H2O.
Figure S25. Unit cell packing diagram for (3∙H2O)2
S18
Figure S26. Molecular structure of the lithium salt of the pincer ligand, 4 (30% thermal
ellipsoids).
S19
Figure S27. Unit cell packing diagram for 4.
S20
Figure S28. Unit cell packing diagram for 5.
S21
Figure S29. Unit cell packing diagram for 6·CH2Cl2·2H2O.
S22