Supporting Information
for
Meta-metallation of N,N-dimethylaniline: contrasting
direct sodium-mediated zincation with indirect sodiationdialkylzinc co-complexation
David R. Armstrong, Liam Balloch*, Eva Hevia, Alan R. Kennedy, Robert E. Mulvey*,
Charles T. O’Hara and Stuart D. Robertson
Address: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde,
Glasgow, G1 1XL, United Kingdom
Email:
David
R.
Armstrong
-
[email protected];
Liam
Balloch*
-
[email protected]; Robert E. Mulvey* - [email protected]
* Corresponding author
Computational details and NMR spectra for compounds 3, 4, 5 and 6
DFT calculations were carried out using the Gaussian G03 computational package [1]. The
B3LYP density functionals [2,3] were used along with the 6-311G(d,p) basis set [4,5]. After
the geometry optimisation of each molecule, a frequency analysis was carried out. The
resulting calculated zero-point energy was added to the electronic energy and this is the
energy value quoted below.
S1
o-NaC6H4-NMe2
Principal bond lengths (Å) and angles (°)
Na-N
2.289 Å
C-Na-N 63.0°
Na-C
2.439 Å
Na-N-C 85.6°
Na-Ci
2.758 Å
N-C-C
117.8°
Ci-N
1.487 Å
C-C-Na
93.6°
m-NaC6H4-NMe2
Principal bond lengths (Å) and angles (°)
Na-C
2.301 Å
Na-C-C
122.8 ° 120.5 °
p-NaC6H4-NMe2
Principal bond lengths (Å) and angles (°)
Na-C
2.301 Å
Na-C-C
123.0 °
S2
C6H5-N(Me)CH2Na
Principal bond lengths (Å) and angles (°)
Na-C
2.387 Å
N-Ci
1.371 Å
Na..Ci
3.023 Å
N-CMe
1.469 Å 1.451Å
Na..Co
2.862 Å
Na..N
2.959 Å
Energies/au
o-NaC6H4-NMe2
-527.821237
m-NaC6H4-NMe2
-527.807529
p-NaC6H4-NMe2
-527.807352
C6H5-N(Me)CH2Na
-527.818668
Relative energies/kcal mol-1
ortho:meta:para:methyl
0.00:8.60:8.71:1.61
S3
[o-NaC6H4-NMe2(TMEDA)]
Principal bond lengths (Å) and angles (°)
Na-Ntm
2.521 Å 2.533 Å
Na-N
2.501 Å
Na-C
2.357 Å
Ci-N
1.488 Å
Ntm-Na-Ntm
74.5 °
C-Na-N
61.1 °
Na-N-C
86.8 °
N-C-C
117.5 °
C-C-Na
94.6 °
[m-NaC6H4-NMe2(TMEDA)]
Principal bond lengths (Å) and angles (°)
Na-C
2.356 Å
Na-N
2.513 Å 2.517 Å
Na-C-C
119.5 ° 125.4 °
N-Na-N
74.7 °
S4
[p-NaC6H4-NMe2(TMEDA)]
Principal bond lengths (Å) and angles (°)
Na-C
2.351 Å
Na-N
2.518 Å 2.517 Å
Na-C-C
123.8 ° 123.7 °
N-Na-N
74.6 °
[{C6H5-N(Me)CH2Na}(TMEDA)]
Principal bond lengths (Å) and angles (°)
Na-C
2.424 Å
Na..Ci
3.118 Å
Na..Co
2.963 Å
N-CMe
1.489 Å 1.448 Å
Na-N
2.518 Å 2.527 Å
N-Na-N
74.8 °
S5
Energies/au
[o-NaC6H4-NMe2(TMEDA)]
-875.471777
[m-NaC6H4-NMe2(TMEDA)]
-875.460731
[p-NaC6H4-NMe2(TMEDA)]
-875.460371
[{C6H5-N(Me)CH2Na}(TMEDA)]
-875.469626
Relative energies kcal mol-1
ortho:meta:para:methyl
0.00:6.93:7.15:1.35
Energies of the reactions
TMEDA·BuNa + C6H5-NMe2 → BuH + TMEDA·NaC6H4-NMe2
[o-NaC6H4-NMe2(TMEDA)]
ΔE = -12.74 kcal mol-1
[m-NaC6H4-NMe2(TMEDA)]
ΔE = -5.81 kcal mol-1
[p-NaC6H4-NMe2(TMEDA)]
ΔE = -5.59 kcal mol-1
[{C6H5-N(Me)CH2Na}(TMEDA)]
ΔE = -11.39 kcal mol-1
S6
[o-NaC6H4-NMe2(TMEDA)]2
Principal bond lengths (Å) and angles (°)
Na-Ntm
2.604 Å 2.674 Å
Na-N
2.662 Å
Na-C
2.594 Å 2.605 Å
Ci-N
1.461 Å
Ntm-Na-Ntm
70.6 °
C-Na-N
55.6 °
Na-N-C
85.3 °
N-C-C
117.0 °
C-C-Na
88.8 °
C-Na-C
105.3 °
Na-C-Na
74.7 °
[m-NaC6H4-NMe2(TMEDA)]2
Principal bond lengths (Å) and angles (°)
Na-C
2.571 Å 2.532 Å
Na-N
2.546 Å 2.546 Å
Na-C-Na
72.1 °
C-Na-C
107.9 °
N-Na-N
74.7 °
S7
[p-NaC6H4-NMe2(TMEDA)]2
Principal bond lengths (Å) and angles (°)
Na-C
2.551 Å 2.548 Å
Na-N
2.545 Å 2.544 Å
Na-C-Na
69.1 °
C-Na-C
110.9 °
N-Na-N
74.7 °
[{C6H5-N(Me)CH2Na}(TMEDA)]2
Principal bond lengths (Å) and angles (°)
Na-C
2.598 Å 2.563 Å
Na..Ci
3.632 Å
Na..Co
4.320 Å
N-CMe
1.496 Å 1.459 Å
Na-N
2.581 Å 2.587 Å
N-Na-N
73.5 °
Na-C-Na
74.1 °
C-Na-C
105.9 °
S8
Energies/au
[o-NaC6H4-NMe2(TMEDA)]2
-1750.978739
[m-NaC6H4-NMe2(TMEDA)]2
-1750.971326
[p-NaC6H4-NMe2(TMEDA)]2
-1750.969999
[{C6H5-N(Me)CH2Na}(TMEDA)]2
-1750.965031
Relative energies/kcal mol-1
ortho:meta:para:methyl
0.00:4.65:5.48:8.60
Energies of the reactions
2 TMEDA·BuNa + 2 C6H5-NMe2 → 2 BuH + [TMEDA·NaC6H4-NMe2]2
[o-NaC6H4-NMe2(TMEDA)]2
ΔE = -47.55 kcal mol-1
[m-NaC6H4-NMe2(TMEDA)]2
ΔE = -42.90 kcal mol-1
[p-NaC6H4-NMe2(TMEDA)]2
ΔE = -42.07 kcal mol-1
[{C6H5-N(Me)CH2Na}(TMEDA)]2
ΔE = -38.95 kcal mol-1
S9
[(TMEDA)Na(µ-TMP)(µ-m-C6H4-NMe2)Zn(tBu)]
Principal bond lengths (Å)
Na-C
2.594
Na…C
3.070 3.212
Na-NTMP
2.454
Na-NTMEDA
2.602 2.606
Zn-Cbr
2.084
Zn-Cter
2.040
Zn-N
2.054
[(TMEDA)Na(µ-TMP)(µ-p-C6H4-NMe2)Zn(tBu)]
Principal bond lengths (Å)
Na-C
2.596
Na…C
3.178 3.239
Na-NTMP
2.445
Na-NTMEDA
2.599 2.591
Zn-Cbr
2.083
Zn-Cter
2.042
Zn-N
2.055
S10
[(TMEDA)Na(µ-TMP)(µ-o-C6H4-NMe2)Zn(tBu)]
Principal bond lengths (Å)
Na-C
2.747
Na…C
2.937
Na-N
2.780
Na-NTMP
2.497
Na-NTMEDA
2.651 2.807
Zn-Cbr
2.107
Zn-Cter
2.055
Zn-N
2.048
Energies/au
[(TMEDA)Na(µ-TMP)(µ-m-C6H4-NMe2)Zn(tBu)]
-3221.012984
[(TMEDA)Na(µ-TMP)(µ-p-C6H4-NMe2)Zn(tBu)]
-3221.011929
[(TMEDA)Na(µ-TMP)(µ-o-C6H4-NMe2)Zn(tBu)]
-3221.006092
[(TMEDA)Na(µ-TMP)(µ-C6H5-N(CH2)Me)Zn(tBu)] -3220.998630
Relative energies/kcal mol-1
meta:para:ortho:methyl
0.00:0.66:4.32:9.01
S11
Energies of the reactions
[(TMEDA)Na(µ-TMP)(µ-tBu)Zn(tBu)] + C6H5-NMe2 →
BuH + [(TMEDA)Na(µ-TMP)(µ-C6H4-NMe2)Zn(tBu)]
[(TMEDA)Na(µ-TMP)(µ-m-C6H4-NMe2)Zn(tBu)]
ΔE =-21.46 kcal mol-1
[(TMEDA)Na(µ-TMP)(µ-p-C6H4-NMe2)Zn(tBu)]
ΔE=-20.80 kcal mol-1
[(TMEDA)Na(µ-TMP)(µ-o-C6H4-NMe2)Zn(tBu)]
ΔE=-17.13 kcal mol-1
[(TMEDA)Na(µ-TMP)(µ-C6H5-N(CH2)Me)Zn(tBu)]
ΔE=-12.45 kcal mol-1
S12
NMR spectroscopic analysis
 Key
meta
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
6.179
6.5
1.016
2.003
7.0
2.000
7.5
para
2.529
ortho
7.228
7.225
7.210
7.160
6.794
6.793
6.782
6.780
6.778
6.765
6.630
6.628
6.624
6.614
6.613
6.611
N,N-dimethylaniline
Spectrum 1. 1H NMR (400.13 MHz, 300 K) spectrum of N,N-dimethylaniline in C6D6 solution.
S13
ppm
7.0
6.9
6.8
6.7
6.6
ppm
6.5
2.003
7.1
1.016
7.2
6.630
6.628
6.624
6.614
6.613
6.611
6.794
6.793
6.782
6.780
6.778
6.765
7.160
7.243
7.228
7.225
7.210
7.3
2.000
7.4
170
160
150
140
130
120
110
40.194
116.946
112.973
129.284
128.195
128.000
127.805
150.975
Spectrum 2. Aromatic region of 1H NMR spectrum of N,N-dimethylaniline in C6D6 solution.
100
90
80
70
60
50
40
30
20
10
Spectrum 3. 13C {1H} NMR (100.62 MHz, 300 K) spectrum of N,N-dimethylaniline in C6D6 solution.
S14
ppm
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
1.380
2.0
1.5
1.0
0.5
6.396
6.5
0.959
2.010
2.000
7.0
2.711
2.706
7.107
7.092
7.089
7.075
6.630
6.615
6.600
6.576
6.560
6.559
7.5
Spectrum 4. 1H NMR (400.13 MHz, 300 K) spectrum of N,N-dimethylaniline in C6D12 solution.
S15
ppm
7.0
6.9
6.8
6.7
6.6
6.5
6.4
6.3
6.2
6.1
ppm
2.010
7.1
0.959
7.2
6.630
6.615
6.600
6.576
6.560
6.559
7.107
7.092
7.089
7.075
7.3
2.000
7.4
160
150
140
130
120
110
100
90
80
70
60
50
40
26.703
26.552
26.400
26.248
26.096
40.619
117.285
113.231
129.405
151.292
Spectrum 5. Aromatic region of 1H NMR spectrum of N,N-dimethylaniline in C6D12 solution.
30
20
10
Spectrum 6. 13C {1H} NMR (100.62 MHz, 300 K) spectrum of N,N-dimethylaniline in C6D12 solution.
S16
ppm
8.2
8.0
7.8
7.6
5.0
7.4
4.5
4.0
3.5
7.2
7.0
5.362
16.027
5.5
6.8
6.6
2.340
6.545
6.0
1.019
6.5
6.809
6.804
6.789
6.786
6.771
6.767
6.612
6.596
6.579
6.559
7.0
7.092
7.074
7.070
7.051
7.795
7.792
7.780
7.777
1.019
2.340
7.5
0.194
1.000
8.4
0.194
1.000
8.0
3.0
2.5
2.0
1.5
1.0
6.4
0.5 ppm
Spectrum 7. 1H NMR (400.13 MHz, 300 K) spectrum of 3 in C6D12 solution.
6.2
ppm
Spectrum 8. Aromatic region of 1H NMR spectrum of 3 in C6D12 solution.
S17
0.907
0.890
0.873
1.380
1.286
2.222
2.040
2.855
2.832
7.795
7.792
7.780
7.777
7.092
7.074
7.070
7.051
6.809
6.804
6.789
6.786
6.771
6.767
6.612
6.596
6.579
6.559
180
160
140
120
100
80
60
40
26.782
26.591
26.400
26.210
26.020
45.984
44.994
58.582
113.281
111.499
129.286
124.569
120.185
142.699
164.061
182.327
200
20
ppm
0
Spectrum 9. 13C {1H} NMR (100.62 MHz, 300 K) spectrum of 3 in C6D12 solution.
S18
5.5
5.0
4.5
4.0
3.5
3.0
2.0
1.380
1.292
0.909
0.898
0.895
0.881
2.044
1.912
2.5
1.5
1.0
0.5
0.600
1.896
6.0
6.886
6.5
3.034
2.000
7.0
2.746
7.098
7.083
7.080
7.066
6.616
6.602
6.600
6.589
6.587
6.585
6.583
6.579
6.569
6.567
6.566
7.5
Spectrum 10. 1H NMR (400.13 MHz, 300 K) spectrum of mother liquor following isolation of 3 in
C6D12 solution.
S19
ppm
6.616
6.602
6.600
6.589
6.587
6.585
6.583
6.579
6.569
6.567
6.566
7.098
7.083
7.080
7.066
7.0
6.9
6.8
6.7
6.6
6.5
6.4
ppm
3.034
7.1
2.000
7.2
4.5
4.0
3.5
3.0
2.038
1.917
5.0
2.5
2.0
12.994
4.190
5.5
2.538
5.740
5.723
5.706
6.0
1.873
6.5
2.037
7.0
2.029
7.5
1.000
7.160
6.789
6.772
6.769
6.751
6.511
6.493
6.490
Spectrum 11. Aromatic region of 1H NMR spectrum of mother liquor following isolation of 3 in C6D12
solution.
1.5
1.0
0.5
ppm
Spectrum 12. 1H NMR (400.13 MHz, 300 K) spectrum from the reaction of 3 with toluene in C6D6
solution.
S20
7.0
6.8
6.4
5.740
5.723
5.706
6.511
6.493
6.490
6.6
6.2
6.0
5.8
5.6
5.4
5.2
ppm
1.000
7.2
2.037
7.4
2.029
7.6
6.789
6.772
6.769
6.751
7.160
7.8
Spectrum 13. Aromatic region of 1H NMR spectrum from the reaction of 3 with toluene in C6D6
solution.
S21
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
Spectrum 14. 1H NMR (400.13 MHz, 300 K) spectrum from the reaction of 1 and N,N-dimethylaniline
with iodine in C6D6 solution.
S22
ppm
2.316
2.361
2.463
2.542
meta
N,N-dimethylaniline
para
ortho
2.40
2.35
2.30
2.25
ppm
6.011
2.45
1.575
2.50
0.520
2.55
3.194
2.60
Spectrum 15. Aliphatic region of 1H NMR spectrum from the reaction of 1 and N,N-dimethylaniline
with iodine in C6D6 solution.
S23
7.5
7.4
7.3
7.2
7.1
7.0
6.9
6.8
6.6
*
6.5
6.4
6.3
6.2
0.621
*
0.978
*
*
0.108
6.7
1.162
*
0.957
*
0.582
*
1.117
7.6
*
0.980
7.7
0.130
*
1.134
7.8
0.036
7.9
0.584
0.096
*
*
*
*
6.1
6.0
ppm
Spectrum 16. Aromatic region of 1H NMR spectrum from the reaction of 1 and N,N-dimethylaniline
with iodine in C6D6 solution.
S24
7.430
7.412
7.362
7.344
7.227
7.212
7.209
7.194
7.160
7.145
7.141
7.137
7.060
7.044
6.987
6.982
6.979
6.774
6.760
6.745
6.743
6.727
6.714
6.698
6.682
6.617
6.615
6.599
6.478
6.474
6.462
6.460
6.447
6.444
6.396
6.394
6.379
6.377
6.354
6.350
6.338
6.333
6.141
6.123
5.950
5.932
7.760
7.757
7.744
7.741
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
ppm
155
150
145
140
137.782
130.649
129.279
128.195
128.000
127.805
125.503
125.471
125.437
125.124
121.398
121.368
121.336
121.302
121.270
121.237
121.032
120.832
120.374
117.242
116.942
116.907
116.877
115.028
114.962
114.717
113.364
113.034
113.003
112.968
112.933
112.902
112.533
111.844
111.812
111.778
111.710
141.708
140.455
151.751
150.919
150.079
Spectrum 17. 13C NMR (100.62 MHz, 300 K) spectrum from the reaction of 1 and N,N-dimethylaniline
with iodine in C6D6 solution.
135
130
125
120
115
110
105
ppm
Spectrum 18. Aromatic region of 13C NMR spectrum from the reaction of 1 and N,N-dimethylaniline
with iodine in C6D6 solution.
S25
Spectrum 19. Aromatic region of 1H-1H COSY NMR spectrum from the reaction of 1 and N,Ndimethylaniline with iodine in C6D6 solution.
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5 ppm
Spectrum 20. 1H NMR (400.13 MHz, 300 K) spectrum of 4 and 5 in C6D6 solution.
S26
7.0
6.8
0.283
7.2
1.305
23.080
16.691
18.749
2.0
1.044
7.4
0.289
7.6
0.286
7.8
7.176
7.172
7.162
7.159
7.154
7.138
7.134
7.078
7.076
7.059
7.043
7.041
7.025
7.020
7.006
7.005
7.002
6.987
6.982
6.870
6.867
6.851
6.835
6.833
6.735
6.715
6.611
6.591
2.5
0.976
8.0
8.388
0.815
0.667
3.0
2.543
8.2
0.266
8.4
1.000
8.039
8.035
8.022
8.018
7.879
7.875
7.862
7.858
3.5
1.5
1.0
6.6
6.4
ppm
Spectrum 21. Aliphatic region of 1H NMR spectrum of 4 and 5 in C6D6 solution.
6.2
ppm
Spectrum 22. Aromatic region of 1H NMR spectrum of 4 and 5 in C6D6 solution.
S27
1.762
1.738
1.659
1.646
1.634
1.589
2.697
3.269
Spectrum 23. Aromatic region of 1H-1H COSY NMR spectrum of 4 and 5 in C6D6 solution.
S28
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5 ppm
2.326
2.454
2.523
Spectrum 24. 1H NMR (400.13 MHz, 300 K) spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
ortho
N,N-dimethylaniline
para
2.50
2.48
2.46
2.44
2.42
2.40
2.38
2.36
2.34
2.32
ppm
0.298
2.52
6.014
2.54
0.851
2.56
Spectrum 25. Aliphatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
S29
7.0
6.9
6.8
6.7
6.6
6.5
6.4
6.3
ppm
6.2
0.090
7.1
*
0.257
7.2
0.877
7.3
0.107
7.4
0.940
7.5
*
*
0.242
7.6
0.103
7.7
0.903
7.8
*
0.915
*
*
7.9
*
*
6.141
6.118
7.001
6.998
6.981
6.963
6.960
6.804
6.786
6.768
6.733
6.730
6.713
6.710
6.695
6.640
6.619
6.467
6.463
6.448
6.445
6.429
6.426
7.247
7.242
7.229
7.225
7.212
7.207
7.160
7.461
7.456
7.443
7.439
7.780
7.777
7.760
7.757
*
Spectrum 26. Aromatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
ppm
Spectrum 27. 13C NMR (100.62 MHz, 300 K)spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
S30
155
150
145
140
135
130
125
120
115
113.083
115.003
129.307
129.149
129.113
129.076
128.241
128.119
128.000
127.882
127.759
125.159
125.123
125.087
125.057
120.850
120.814
120.779
117.138
140.545
140.509
140.473
137.845
155.384
160
110
105
ppm
Spectrum 28. Aromatic region of 13C NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
Spectrum 29. Aromatic region of 1H-1H COSY NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline and tBu2Zn with iodine in C6D6 solution.
S31
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
ppm
1.2
1.0
ppm
0.8
10.012
1.059
1.052
1.049
0.980
0.951
0.929
0.923
1.4
1.196
1.371
1.6
11.913
1.8
3.601
1.740
1.729
2.0
2.966
2.153
2.2
15.045
2.4
4.859
2.6
6.082
2.8
2.307
2.752
2.696
Spectrum 30. 1H NMR (400.13 MHz, 300 K) spectrum of 6 in d8-THF solution.
Spectrum 31. Aliphatic region of 1H NMR spectrum of 6 in d8-THF solution.
S32
6.935
6.932
6.931
6.929
6.916
6.915
6.902
6.901
6.899
6.822
6.806
6.763
6.761
6.747
6.733
7.2
7.1
7.0
6.9
6.8
6.7
6.6
ppm
1.229
7.3
1.021
7.4
1.040
7.491
7.477
7.5
1.000
7.6
Spectrum 32. Aromatic region of 1H NMR spectrum of 6 in d8-THF solution.
S33
200
180
160
140
120
100
80
60
40
20
ppm
0
65
60
55
50
45
40
35
30
25
20.632
19.791
25.560
25.477
25.388
25.305
25.215
25.131
25.042
36.382
36.172
36.075
35.722
35.334
40.705
46.844
46.206
45.220
53.072
58.923
67.578
67.402
67.227
Spectrum 33. 13C NMR (100.62 MHz, 300 K) spectrum of 6 in d8-THF solution.
20
15
ppm
Spectrum 34. Aliphatic region of 13C NMR spectrum of 6 in d8-THF solution.
S34
175
170
155
150
145
140
135
130
125
120
114.852
113.947
122.240
120.967
160
125.808
125.537
165
141.172
160.079
180
165.045
185
115
110
105 ppm
Spectrum 35. Aromatic region of 13C NMR spectrum of 6 in d8-THF solution.
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5 ppm
Spectrum 36. 1H NMR (400.13 MHz, 300 K) from the reaction of BuNa·TMEDA, N,N-dimethylaniline,
tBu2Zn and TMP(H) with iodine in C6D6 solution.
S35
2.262
2.285
2.325
2.455
2.528
ortho
N,N-dimethylaniline
meta
para
2.35
2.30
ppm
2.25
0.429
2.40
0.575
2.45
0.361
2.50
6.000
2.55
1.787
2.60
7.782
7.778
7.762
7.758
7.538
7.519
7.463
7.441
7.253
7.247
7.235
7.231
7.218
7.215
7.213
7.194
7.160
7.141
7.136
7.021
7.016
7.015
7.010
7.002
6.998
6.982
6.980
6.978
6.963
6.960
6.807
6.805
6.803
6.787
6.769
6.767
6.750
6.745
6.735
6.731
6.724
6.715
6.711
6.694
6.675
6.641
6.639
6.634
6.619
6.617
6.467
6.463
6.448
6.445
6.429
6.426
6.142
6.119
Spectrum 37. Aliphatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine in C6D6 solution.
*
*
*
*
*
6.9
6.8
6.7
6.6
6.5
6.4
6.3
ppm
6.2
0.104
7.0
0.860
7.1
*
*
0.575
7.2
*
0.943
7.3
0.105
0.891
7.4
0.095
7.5
0.609
7.6
0.133
7.7
0.067
7.8
0.853
7.9
*
* *
0.252
*
0.090
*
Spectrum 38. Aromatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine in C6D6 solution.
S36
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5 ppm
2.286
2.319
2.345
2.361
2.464
2.545
Spectrum 39. 1H NMR (400.13 MHz, 300 K) spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
N,N-dimethylaniline
meta
ortho
para
2.30
2.25
ppm
3.454
2.35
6.000
2.40
0.465
2.45
1.441
2.50
5.385
2.55
7.763
2.60
Spectrum 40. Aliphatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
S37
**
*
6.8
6.7
6.6
6.5
6.4
6.147
6.124
6.3
ppm
6.2
0.660
6.9
*
0.173
7.0
0.965
7.1
0.783
7.2
2.502
7.3
4.038
7.4
1.875
7.5
0.743
7.6
2.735
7.7
*
*
*
0.520
7.8
0.853
7.9
*
*
*
*
0.904
*
6.482
6.479
6.462
6.444
6.358
6.352
6.337
6.331
6.777
6.758
6.742
6.720
6.699
6.679
6.617
6.597
7.229
7.226
7.207
7.189
7.160
7.140
7.135
7.064
7.045
7.017
6.984
6.980
7.435
7.412
7.765
7.762
7.745
*
Spectrum 41. Aromatic region of 1H NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
ppm
Spectrum 42. 13C NMR (100.62 MHz, 300 K) spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
S38
150
145
140
135
130
125
120
115
112.981
111.786
114.977
116.975
121.352
120.819
130.646
130.151
128.242
128.001
127.760
125.530
125.124
133.977
141.718
141.682
140.511
140.475
140.439
140.172
139.142
138.031
137.807
137.770
147.677
151.751
150.920
150.078
155.327
156.736
155
110
ppm
Spectrum 43. Aromatic region of 13C NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
S39
Spectrum 44. Aromatic region of 1H-1H COSY NMR spectrum from the reaction of BuNa·TMEDA, N,Ndimethylaniline, tBu2Zn and TMP(H) with iodine following an overnight reflux in C6D6 solution.
S40
References
1. Gaussian 03, Revision B.0.5; Gaussian, Inc.: Pittsburgh PA, 2003.
2. Becke, A. D. Phys. Rev. A 1988, 38, 3098. doi:10.1103/PhysRevA.38.3098
3. Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1998, 37, 785.
doi:10.1103/PhysRevB.37.785
4. McLean, A. D.; Chandler, G. S. J. Chem. Phys. 1980, 72, 5639. doi:10.1063/1.438980
5. Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650.
doi:10.1063/1.438955
S41