Supporting Information
Group 4 complexes bearing bis(salphen) ligands: Synthesis, characterization
and polymerization studies
Mrinmay Mandal,1 Debashis Chakraborty*1
1
Department of Chemistry, Indian Institute of Technology Patna, Patna-800 013, Bihar, India
Correspondence to: D. Chakraborty (E-mail: dc@iitp.ac.in or debashis.iitp@gmail.com), Tel:
+91-612-2552171. Fax: +91-612-2277383.
FIGURE S1 1H NMR (400 MHz, CDCl3) of Compound 1
FIGURE S2 13C NMR (100 MHz, CDCl3) of Compound 1
FIGURE S3 ESI-Mass Spectrum of Compound 1
FIGURE S4 1H NMR (400 MHz, CDCl3) of Compound 2
FIGURE S5 13C NMR (100 MHz, CDCl3) of Compound 2
FIGURE S6 ESI-Mass Spectrum of Compound 2
FIGURE S7 1H NMR (400 MHz, CDCl3) of Compound 3
FIGURE S8 13C NMR (100 MHz, CDCl3) of Compound 3
FIGURE S9 ESI-Mass Spectrum of Compound 3
FIGURE S10 1H NMR (400 MHz, CDCl3) of Compound 4
FIGURE S11 13C NMR (100 MHz, CDCl3) of Compound 4
FIGURE S12 ESI-Mass Spectrum of Compound 4
FIGURE S13 1H NMR (400 MHz, CDCl3) of Compound 5
FIGURE S14 13C NMR (100 MHz, CDCl3) of Compound 5
FIGURE S15 ESI-Mass Spectrum of Compound 5
FIGURE S16 1H NMR (400 MHz, CDCl3) of Compound 6
FIGURE S17 13C NMR (100 MHz, CDCl3) of Compound 6
FIGURE S18 ESI-Mass Spectrum of Compound 6
FIGURE S19 Representative GPC traces for the polymerization of rac-LA: (a) entry 1, Table 1;
(b) entry 5, Table 1.
FIGURE S20 Representative GPC traces for the polymerization of L-LA: (a) entry 7, Table 1;
(b) entry 12, Table 1.
FIGURE S21 Representative GPC traces for the polymerization of ε-CL: (a) entry 17, Table 1;
(b) entry 18, Table 1.
FIGURE S22 Plot of Mn and Mw/Mn vs. % conversion for rac-LA polymerization at 140 °C
using 2, 4 and 6.
FIGURE S23 Plot of Mn and Mw/Mn vs. % conversion for rac-LA, L-LA and ε-CL
polymerization at 140 ºC (LA) and 80 ºC (ε-CL) using 2.
FIGURE S24 Homonucler decoupled 1H NMR spectra of rac-LA in 15: 1 ratio using by 2 in
CDCl3.
FIGURE S25 Semi-logarithmic plots of rac-LA, L-LA and ε-CL conversion in time initiated by
2: [M]o/[Cat]o/[BnOH] = 200: 1: 2 at 140 ºC (LA) and 80 C (ε-CL).
FIGURE S26 rac-LA conversion vs. time plot using 2, 4 and 6: [rac-LA]o/[Cat]o/[BnOH] =
200: 1: 2 at 140 C.
FIGURE S27 rac-LA, L-LA and ε-CL conversion vs. time plot using 2: [M]o/[Cat]o/[BnOH] =
200: 1: 2 at 140 C (LA) and 80 C (ε-CL).
FIGURE S28 MALDI-TOF of the crude product obtained from a reaction between ε-CL and 2
in the presence of BnOH in ratio 15: 1: 2.
FIGURE S29 1H NMR spectrum of the crude product obtained from a reaction between ε-CL
and 2 in the presence of BnOH in ratio 15: 1: 2.
FIGURE S30 Representative GPC traces for the copolymerization of CHO with CO2: (a) entry
1, Table 2; (b) entry 8, Table 2.
FIGURE S31 Plot of Mn and Mw/Mn vs. % conversion for CHO copolymerization at 50 °C using
2, 4 and 6.
FIGURE S32 MALDI-TOF mass spectrum of PCHC sample produced by 2 at 50 °C and 35 bar
CO2 pressure from CHO and CO2 using TBAB as cocatalyst.
FIGURE S33 Representative TGA trace and derivative plot of PCHC produced by 2 (Table 4,
entry 1).
FIGURE S34 Representative DSC trace of PCHC produced by 2, 2nd heat cycle (Table 4, entry
1).
FIGURE S35 1H NMR spectrum of an aliquot from the reaction mixture of PO/CO2 in CDCl3
(Table 5, entry 1).
FIGURE S36 1H NMR spectrum of an aliquot from the reaction mixture of PO/CO2 in CDCl3
(Table 5, entry 1).
FIGURE S37 13C NMR spectrum of an aliquot from the reaction mixture of SO/CO2 in CDCl3
(Table 5, entry 1).
FIGURE S38 Representative GPC traces for the homopolymerization of CHO: (a) entry 2,
Table 5; (b) entry 4, Table 5.
FIGURE S39 1H NMR (500 MHz, CDCl3) of the crude product obtained from a reaction
between CHO and 2 in 1000: 1 ratio at 80 °C.
FIGURE S40 % conversion vs. time plot for the homopolymerization of CHO at [CHO]o/[C]o =
1000: 1.
FIGURE S41 Plot of activity vs. [MAO]/[cat] ratio for 2, 4 and 6 for ethylene polymerization.
FIGURE S42 Effect of temperature on the activity for the complexes 2, 4 and 6 towards
ethylene polymerization.
M2Cl4(C54H62N404)
M2Cl4(C54H62N404)
H
O
BnO
O
O
O
BnOH
O
M2Cl4(C54H62N404)
BnO O
O
O
BnO
O
O
OM2Cl4(C54H62N404)
H
O
O
O
BnO
O
O
OH
O
O
O
O
BnO
O
OH
O
O
O
O
H
n
O
M= Ti, Zr and Hf
Scheme S1 Polymerization proceeds through the coordination-insertion mechanism for rac-LA
in the presence of BnOH.
M2Cl4(C54H62N404)
O
H
O
BnO
O
M2Cl4(C54H62N404)
O
BnOH
BnO
O
M2Cl4(C54H62N404)
O
OH
H
O
O
BnO
O
O
M2Cl4(C54H62N404)
O
O
BnO
O H
n
M= Ti, Zr and Hf
Scheme S2 Polymerization proceeds through the coordination-insertion mechanism for ε-CL in
the presence of BnOH.
O
Br
Salphen
Cl
TBAB
M
Salphen
Cl
Br
M
Cl
Salphen
M
Cl
Cl
Cl
Cl
OH
O
Cl
M
Br
O
OH
From Water
Salphen
O
Salphen
Cl
CO2
O
O
M
Br
OH
Cl
O
CO2
Cl
Salphen
M
Br
Cl
HO
O
OH
O
O
OH
O
O
Quenching
O
O
n
n
PCHC
M = Ti, Zr or Hf
Scheme S3 Plausible mechanism for the copolymerization of CHO with CO2.
O
O
P
O
C
O
O
O
carbonate backbiting
O
O
O
O
P
[M]
[M]
O
O
O
C
O
alkoxide backbiting
P
O
O
O
O
[M]
O
[M]
P
O
P = propagating polymer chain
Scheme S4 Backbiting reaction of the growing polymer chain: (Top) carbonate anion backbiting,
(bottom) alkoxide anion backbiting.
TABLE S1 Polymerization data for rac-LA, L-LA and ε-CL using 1–6 in 200: 1 (monomer: initiator) ratio.
Entry
Initiator
Monomer
T / oC
1
1
rac-LA
140
Yield
(%)
27
2
2
rac-LA
140
29
3
3
rac-LA
140
4
4
rac-LA
5
5
6
a
a
Mnobs/kg
mol-1
3.77
Mw/Mn
48
3.89
1.48
26
48
3.69
1.54
140
27
48
3.75
1.52
rac-LA
140
23
48
3.35
1.59
6
rac-LA
140
24
48
3.49
1.55
7
2
L-LA
140
28
48
3.95
1.46
8
2
ε-CL
80
26
48
3.66
1.53
Time
/h
48
b
1.50
Time of polymerization measured by quenching the polymerization reaction when all monomer was found
consumed. bMeasured by GPC at 27 °C in THF relative to polystyrene standards with Mark-Houwink corrections for
Mn for ε-CL and LA polymerization.
TABLE S2 Solution polymerization data based on changing ratios in case of rac-LA using 2, 4 and 6 in the
presence of benzyl alcohol at 140 oC.
Mnobs/
kgmol-1
10.52
Mntheo/
kgmol-1
7.315
Mw/Mn
7
Yield
(%)
99
200: 1: 2
12
99
18.02
14.52
1.03
2
400: 1: 2
19
96
32.15
28.94
1.06
4
2
600: 1: 2
30
95
47.05
43.35
1.09
5
2
800: 1: 2
45
93
61.03
57.76
1.13
6
4
100: 1: 2
12
98
7
4
200: 1: 2
18
97
15.55
14.52
1.06
8
4
400: 1: 2
27
95
30.89
28.94
1.09
9
4
600: 1: 2
40
94
45.23
43.35
1.12
10
4
800: 1: 2
57
92
59.05
57.76
1.15
11
6
100: 1: 2
16
97
Entry
Initiator
1
2
[M]/[C]/[BnOH]
ratio
100: 1: 2
2
2
3
a
Time/min
b
8.912
8.017
c
7.315
7.315
1.02
1.05
1.07
a
12
6
200: 1: 2
22
95
15.02
14.52
1.09
13
6
400: 1: 2
33
94
28.52
28.94
1.12
14
6
600: 1: 2
48
93
42.87
43.35
1.15
15
6
800: 1: 2
65
91
57.35
57.76
1.18
Time of polymerization measured by quenching the polymerization reaction when all monomer was found
consumed. bMeasured by GPC at 27 °C in THF relative to polystyrene standards with Mark-Houwink corrections for
Mn for rac-LA polymerization. cMn (theoretical) at 100 % conversion = [M]o/[C]o × mol wt (monomer) + mol wt
(BnOH).