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ElectronicSupportingInformationfor:
Investigationsintothestructure,reactivity,andAACVDofaluminiumandgalliumamidoenoatecomplexes
KristianL.Mears,MalavikaA.Bhide,CarolineE.Knapp*andClaireJ.Carmalt*
DepartmentofChemistry,UniversityCollegeLondon,20GordonSt,London,WC1H0AJ,UK.
*CorrespondingauthorE-mail:[email protected]
Table of Contents A. Thin film analysis S2
B. NMR spectra from reactivity studies S5
C. NMR spectra of complexes S7
D. Crystallographic data S24
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2021
S2
A. Thinfilmanalysis
Fig1:Surveyscanofthinfilmdepositedbycomplex[AlCl(AMEDip)2](3-Al).NoClpresentinsurveyscan(Cl2p3/2=200eV;2p1/2=202eV;Cl2s=270eV).
Fig2:Surveyscanofthinfilmdepositedbycomplex[AlH(AMEDip)2](4-Al).NoClpresentinsurveyscan(Cl2p3/2=200eV;2p1/2=202eV;Cl2s=270eV).
Al2s
Al 2p 1/2 Al 2p 3/2
C 1s
O 1s
O KLL
Al2s
C 1s
O 1s
O KLL
Al 2p 1/2 Al 2p 3/2
S3
Fig3:Surveyscanofthinfilmdepositedbycomplex[GaCl2(AMEiPr)](1-Ga).NoClpresentinsurveyscan(Cl2p3/2=200eV;2p1/2=202eV;Cl2s=270eV).
Fig4:Surveyscanofthinfilmdepositedbycomplex[GaCl(AMEDip)2](3-Ga).NoClpresentinsurveyscan(Cl2p3/2=200eV;2p1/2=202eV;Cl2s=270eV).
Ga 3d 5/2 Ga 3d 3/2
Ga 2p 3/2 Ga 2p 1/2
Ga 3p 3/2 Ga 3p 1/2
Ga 3s
Ga LMM
O 1s
Ga 3d 5/2 Ga 3d 3/2
Ga 2p 3/2 Ga 2p 1/2
Ga 3p 3/2 Ga 3p 1/2
Ga 3s
Ga LMM
O 1s
S4
Fig5.SEMimagesofGa2O3onglass(left)andonquartzafterannealingtreatment(1000°Cinairfor12hours)depositedfrom[GaCl(AMEDip)2],(3-Ga).1µmscalebarinset.
Fig6.XPSanalysisofGa2O3showingtheGa3d5/2,3d3/2,2p3/2and2p1/2states,includingtheO1sstate,depositedfrom[GaCl(AMEDip)2],(3-Ga).
S5
Fig7.UV-vis(transmittance)plotsgeneratedforeachoftheprecursorsdepositedonglass(left)andonquartz(right)afterannealingtreatment(1000°Cinairfor12hoursshowingimprovedtransmissionandtransparencyafterthepost-annealingtreatment.
Fig8.XRDpatternsofAl2O3(left)andGa2O3(right)thinfilmsonquartzwithimprovedcrystallinityafterannealingtreatment(1000°Cinairfor12hours),depositedfrom[AlCl(AMEDip)2],(3-Al)and[GaCl(AMEDip)2],(3-Ga)respectively(0.2gofprecursor).
Fig9.Photographofathinfilmdepositedonglassandquartz(pre-anneal)fromprecursor3-Ga(0.2gofprecursor).
104
116
024
113
119
104
116
401
002
202
104
40
1
311
512
712
401
00
2
202
311
512
Wavelength / nm Wavelength / nm
Tran
smitt
ance
/ %
Tran
smitt
ance
/ %
S6
B. NMRspectrafromreactivitystudies
Fig10.Stacked1HNMRspectraofmagnesium(I)dimers,[Mg(BDIMes)](bottom),[GaCl(AMEDip)2],3-Ga(middle)andtheproductoftheiradditionatambienttemperature(top).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
{GaCl(AMEDip)2} + {MgBDIMes}2
{GaCl(AMEDip)2}
{MgBDIMes}2
S7
Fig11.Stacked1HNMRspectraofmagnesium(I)dimers,[Mg(BDIMes)](bottom),[GaCl(AMEDip)2],3-Ga(lowermiddle),theproductoftheiradditionafterstirringat60°C(uppermiddle)andafterstirringat90°C(top).
C. NMRspectraofcomplexes
Fig12.1HNMRofHAMEDip
0.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
{Mg(BDIMes)}2
{GaCl(AMEDip)2}
{GaCl(AMEDip)2} + {Mg(BDIMes)}2 at 60 °C
{GaCl(AMEDip)2} + {Mg(BDIMes)}2 at 90 °C
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1(ppm)
6.266.283.253.042.012.000.702.001.000.70
1.1
41
.16
1.2
11
.23
1.2
91
.31
1.3
2
1.6
3
3.0
73
.08
3.1
03
.11
3.1
2
4.1
54
.16
4.1
84
.19
4.6
8
7.1
67
.17
7.2
6 C
DC
l37
.28
7.2
97
.31
9.8
6
18,19,20,21
9
6
12,14
8
16,1713
31
1HNMR(500MHz,CDCl3)δ9.86(s,1H),7.29(t,J=
7.7Hz,1H),7.17(d,J=7.6Hz,2H),4.68(s,1H),
4.17(q,J=7.1Hz,2H),3.10(sept,J=6.9Hz,2H),
1.63(s,3H),1.31(t,J=7.1Hz,3H),1.22(d,J=6.9
Hz,6H),1.15(d,J=6.8Hz,6H).
NH1
2
3
4
O5
6 O7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
S8
Fig13.13C{1H}NMRofHAMEDip
Fig14.1H–1HCOSYNMRofHAMEDip
102030405060708090100110120130140150160170180190200f1(ppm)
14
.74
19
.87
22
.78
24
.78
28
.52
58
.85
77
.16
CD
Cl3
12
3.6
5
12
8.3
5
14
7.0
1
17
0.6
9
16,17
12,14
9
613824
18,19,20,21
11,15
NH1
2
3
4
O5
6 O7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
13CNMR(126MHz,CDCl3)δ170.69,147.01,
133.0,128.35,123.65,58.85,28.52,24.78,22.78,
19.87,14.74.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f2(ppm)
20
40
60
80
100
120
140
160
f1(ppm)
13
12,14
3 8 16,17 6 9
18,19,20,21
4
2
11,15
1312,14
8
16,1718,19,20,21
69
S9
Fig15.1H–13CHSQCNMRofHAMEDip
Fig16.1H–13CHMBCNMRofHAMEDip
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f2(ppm)
0
20
40
60
80
100
120
f1(ppm)
13
12,14
3 8 16,17 6 9
18,19,20,21
1312,14
8
16,1718,19,20,21
6
9
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f2(ppm)
1
2
3
4
5
6
7
8
f1(ppm)
13
12,14
3 8 16,17 6 9
18,19,20,21
1312,14
3
8
16,17
6
918,19,20,21
S10
Fig17.1HNMRof[AlCl2(AMEiPr)](1-Al),solvents(hexaneanddiethylether),markedwithanasterisk(red)andsmallquantitiesofunidentifieddecompositionproduct(blue)
Fig18.13C{1H}NMRof[AlCl2(AMEiPr)],(1-Al)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
2.986.982.190.462.511.35
0.8
40
.86
0.8
8
1.2
71
.29
1.5
2
3.5
23
.64
3.6
73
.69
3.7
1
4.4
9
7.1
6 C
6D
6
12,13
7 106
9
11
1 O2
Al3
N4
5
6
7
O8
9
10
11
1213
Cl14
Cl15
1HNMR(300MHz,C6D6)δ4.49(s,1H),3.68(q,J=7.1Hz,2H)3.52(m,1H),
1.52(s,3H),1.28(d,J=6.6Hz,6H),0.86(t,J=7.1Hz,3H).
* * * *
-100102030405060708090100110120130140150160170180190200210f1(ppm)
14
.22
14
.36
23
.37
23
.51
25
.78
50
.13
63
.08
83
.37
12
8.0
6 C
6D
6
17
0.7
8
17
7.3
0
12,137
11 109651
1 O2
Al3
N4
5
6
7
O8
9
10
11
1213
Cl14
Cl15 13CNMR(75MHz,C6D6)δ177.30,170.78,83.37,68.20,50.13,25.78,23.51,
23.37,14.36,14.22.
S11
Fig19.1H–1H COSYNMRof[AlCl2(AMEiPr)](1-Al)
Fig20.1H–13C HSQCNMRof[AlCl2(AMEiPr)](1-Al)
0.00.51.01.52.02.53.03.54.04.55.0f2(ppm)
0
1
2
3
4
f1(ppm)
6 9 11 7 12,13 10
6
911
7
12,13
10
1 O2
Al3
N4
5
6
7
O8
9
10
11
1213
Cl14
Cl15
0.00.51.01.52.02.53.03.54.04.55.05.56.0f2(ppm)
0
10
20
30
40
50
60
70
80
90
f1(ppm)
6 9 11 7 12,13 10
6
9
11
712,13
10
1 O2
Al3
N4
5
6
7
O8
9
10
11
1213
Cl14
Cl15
S12
Fig21.1H NMRof[AlCl(AMEiPr)2](2-Al),solvents(hexaneanddiethylether),markedwitharedasterisk
Fig22.13C{1H} NMRof[AlCl(AMEiPr)2](2-Al),
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
6.3312.076.034.462.172.00
1.0
31
.06
1.0
8
1.3
41
.36
1.7
4
3.9
23
.95
3.9
73
.99
4.0
64
.08
4.1
04
.13
4.1
54
.17
4.2
0
4.7
0
7.1
6 C
6D
6
13,1522,23,25,26
18,20
6,9
17,19
21,24
1 O2
Al3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
25
26
1HNMR(300MHz,C6D6)δ4.70(s,2H),4.13(hept,J
=6.5Hz,2H),3.96(q,J=7.1Hz,4H),1.74(s,6H),
1.35(d,J=7.0Hz,12H),1.06(t,J=7.1Hz,6H).
0102030405060708090100110120130140150160170180190200210f1(ppm)
14.75
23.07
24.01
50.38
61.70
82.02
170.63
174.31
204.11
209.91
22,23,25,26
18,2017,198
6,9 21,2410 5 13,151
13CNMR(75MHz,C6D6)δ209.91,204.11,174.31,170.63,82.02,61.70,24.01,
23.07,14.75.
1 O2
Al3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
25
26
*
S13
Fig23.1H–1H COSY NMRof[AlCl(AMEiPr)2](2-Al)
Fig24.1H NMRof[AlCl(AMEDip)2](3-Al)
0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.0f2(ppm)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
f1(ppm)
6,9 21,24
17,19
13,15 22,23,25,26
18,20
6,9
21,2417,19
13,15
22,23,25,26
18,20
1 O2
Al3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
25
26
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
6.0312.445.795.586.002.084.522.041.936.55
0.8
50
.87
0.8
9
1.1
01
.13
1.2
61
.29
1.4
01
.52
1.5
4
2.5
42
.56
2.5
72
.58
2.6
02
.61
2.6
22
.64
3.1
73
.20
3.2
23
.24
3.2
53
.27
3.2
73
.29
3.3
03
.31
3.3
23
.33
3.3
63
.54
3.5
73
.59
3.6
13
.63
3.6
53
.68
4.8
6
7.0
27
.04
7.0
47
.05
7.0
67
.07
7.1
6 C
6D
6
13,15
40,41,43,44
24,25,26,29,30,31
18,20
37,38
34,35
6,9
1739,42
33,36 19
1 O2
Al3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
25 26
27
28
29
3031
32
33
34
35
36
37
38
39
40
41
42
43
44
1HNMR(300MHz,C6D6)δ7.08–6.99(m,6H),4.86(s,2H),3.61(m,
4H),3.33–3.17(m,4H),2.59(dq,J=10.7,7.1Hz,2H),1.53(d,J=6.6
Hz,6H),1.40(s,6H),1.27(d,J=6.8Hz,6H),1.12(d,J=6.9Hz,12H),
0.87(t,J=7.1Hz,6H).
S14
Fig25.13C{1H} NMRof[AlCl(AMEDip)2](3-Al)
Fig26.1H–1H COSY NMRof[AlCl(AMEDip)2](3-Al)
0102030405060708090100110120130140150160170180f1(ppm)
14
.50
24
.04
24
.20
24
.80
25
.72
25
.87
27
.93
29
.02
60
.07
82
.06
12
3.3
11
24
.30
12
5.7
01
28
.06
C6
D6
14
3.4
31
44
.58
14
7.2
1
17
0.6
1
17
5.7
0
13,15 18,20
40,4137,3834,35
6,926,3124,29
43,44
25,30
5,8
33,36
17,1923,2827,32
39,42
1,10
21,22
1 O2
Al3
N45
6N
7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
3536
37
38
39
40
41 42
43
44
13CNMR(75MHz,C6D6)δ175.70,170.61,
147.21,144.58,143.43,125.70,124.30,123.31,
82.06,60.07,29.02,27.93,25.87,25.72,24.80,
24.20,24.04,14.50.
242526272829f1(ppm)
24
.04
24
.20
24
.80
25
.72
25
.87
27
.93
29
.02
13,15 40,41 37,3834,35
43,44
33,36 39,42
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
1
2
3
4
5
6
7
f1(ppm)
24,25,26,29,30,31 6,9 33,36 17
39,42
19 34,35
13,15
37,38
40,41,43,44
18,20
24,25,26,29,30,31
6,9
33,36
1739,42
19
34,3513,15
37,3840,41,43,44
18,20
1 O2
Al3
N45
6N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
3536
37
38
39
40
41 42
43
44
S15
Fig27.1H–13C HSQC NMRof[AlCl(AMEDip)2](3-Al)
Fig28.1H NMRof[AlH(AMEDip)2](4-Al)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
20
40
60
80
100
120
140
160
180
200
f1(ppm)
24,25,26,29,30,31 6,9 33,36 17
39,42
19 34,35
13,15
37,38
40,41,43,44
18,20
1,105,8
21,22 27,3223,28
25,3026,3124,29
6,9
17,19
33,36 39,42 13,15 43,4440,4134,35 37,38
18,20
1 O2
Al3
N45
6N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
3536
37
38
39
40
41 42
43
44
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
5.9811.905.9111.801.982.023.982.006.04
0.8
00
.83
0.8
5
1.1
21
.15
1.1
7
1.3
11
.33
1.3
7
2.5
12
.53
2.5
42
.55
2.5
72
.58
2.5
92
.61
3.1
23
.15
3.1
63
.17
3.1
83
.19
3.2
13
.23
3.3
03
.33
3.3
53
.37
3.3
93
.42
3.4
43
.47
3.4
93
.51
3.5
3
4.8
0
6.9
96
.99
7.0
17
.01
7.0
37
.03
7.0
37
.05
7.0
57
.16
C6
D6
13,1537,38
40,41,43,44
24,25,26,29,30,31
18,20
34,35
6,9
33,36,39,4219
17
1 O2
Al3
N4
5
6
N7
8
9
10O11H
12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
35
36
37
38
39
40
41
42
43
44
1HNMR(300MHz,C6D6)δ7.08–6.96(m,6H),4.80(s,2H),3.42(dhept,J=
27.4,6.9Hz,4H),3.18(dq,J=10.5,7.1Hz,2H),2.56(dq,J=10.7,7.2Hz,
2H),1.37(s,6H),1.33(s,6H),1.32(d,J=6.8Hz,6H),1.20–1.09(m,12H),
0.83(t,J=7.1Hz,6H).
S16
Fig29.13C{1H} NMRof[AlH(AMEDip)2](4-Al)
Fig30.1H–1H COSY NMRof[AlH(AMEDip)2](4-Al)
0102030405060708090100110120130140150160170180f1(ppm)
14
.50
24
.04
24
.20
24
.80
25
.72
25
.87
27
.93
29
.02
60
.07
82
.06
12
3.3
11
24
.30
12
5.7
01
28
.06
C6
D6
14
3.4
31
44
.58
14
7.2
1
17
0.6
1
17
5.7
0
13,15 18,20
40,4137,3834,35
6,926,3124,29
43,44
25,30
5,8
33,36
17,1923,3227,28
39,42
1,10
21,22
1 O2
Al3
N4
5
6
N7
8
9
10O11
H12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
35
36
37
38
39
40
41
42
43
44
23.524.024.525.025.526.026.527.027.528.028.529.0f1(ppm)
24
.04
24
.20
24
.80
25
.72
25
.87
27
.93
29
.02
13,1540,41 37,38
34,3543,44
33,36 39,4213CNMR(75MHz,C6D6)δ
175.70,170.61,147.21,144.58,
143.43,125.70,124.30,123.31,
82.06,60.07,29.02,27.93,
25.87,25.72,24.80,24.20,
24.04,14.50.
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
1
2
3
4
5
6
7
f1(ppm)
24,25,26,29,30,31 6,9 33,36,39,42
19
17 13,15
37,38
34,35
40,41,43,44
18,20
24,25,26,29,30,31
6,9
33,36,39,4219
17
13,15 37,38 34,3540,41,43,44
18,20
1 O2
Al3
N4
5
6
N7
8
9
10O11
H12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
35
36
37
38
39
40
41
42
43
44
S17
Fig31.1H–13C HSQC NMRof[AlH(AMEDip)2](4-Al)
Fig32.1H NMRof[GaCl2(AMEiPr)2](1-Ga)
Fig33.13C{1H} NMRof[GaCl2(AMEiPr)2](1-Ga)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
20
40
60
80
100
120
140
160
180
200
f1(ppm)
24,25,26,29,30,31 6,9 33,36,39,42
19
17 13,15
37,38
34,35
40,41,43,44
18,20
1,105,8
21,22 27,2823,32
25,30 26,3124,29
6,9
17,19
33,36 39,42 13,1543,44 40,41 34,35 37,38
18,20
1 O2
Al3
N4
5
6
N7
8
9
10O11
H12
13
O14
15
O16
17
18
19
20
21
22
23
24
2526
27
28
29
3031
32
33
34
35
36
37
38
39
40
41
42
43
44
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1(ppm)
2.999.001.001.950.89
0.7
70
.79
0.8
0
1.1
91
.20
1.2
1
3.2
73
.28
3.3
03
.31
3.3
23
.34
3.3
53
.63
3.6
43
.66
3.6
7
4.4
2
7.1
6 C
6D
6
9,12,13
8
17
11
1
2 N3
O45
O6
7
8
9
Ga10
11
12
13
Cl14
Cl15
1HNMR(500MHz,C6D6)δ4.42(s,1H),3.65(q,J=7.1
Hz,3H),3.31(hept,J=6.6Hz,1H),1.23–1.17(m,9H),
0.79(t,J=7.1Hz,3H).
0102030405060708090100110120130140150160170180f1(ppm)
14
.12
22
.48
23
.73
50
.91
62
.61
82
.27
12
8.0
6 C
6D
6
17
2.3
4
17
4.0
9
12,131 8117
9
5 2
1
2 N3
O45
O6
7
8
9
Ga10
11
12
13
Cl14
Cl15
13CNMR(126MHz,C6D6)δ174.09,172.34,82.27,62.61,50.91,23.73,22.48,
14.12.
S18
Fig34.1H–1H COSY NMRof[GaCl2(AMEiPr)2](1-Ga)
Fig35.1H–13C HSQC NMRof[GaCl2(AMEiPr)2](1-Ga)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
1
2
3
4
5
6
7
f1(ppm)
1 7 11 9,12,13 8
1
7
11
9,12,13
8
1
2 N3
O45
O6
7
8
9
Ga10
11
12
13
Cl14
Cl15
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
20
40
60
80
100
120
140
160
180
200f1(ppm)
1 7 11 9,12,13 8
52
1
7
11
12,13 98
1
2 N3
O45
O6
7
8
9
Ga10
11
12
13
Cl14
Cl15
S19
Fig36.1HNMRof[GaCl(AMEiPr)2](2-Ga),solvents(hexaneanddiethylether),markedwithanasterisk(red)andsmallquantitiesofunidentifieddecompositionproduct(blue)
Fig37.13C{1H}NMRof[GaCl(AMEiPr)2](2-Ga)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
12.006.905.301.614.551.53
0.8
20
.84
1.0
61
.08
1.1
0
1.5
2
3.1
13
.13
3.1
53
.16
3.1
73
.18
3.1
93
.20
3.2
13
.22
3.2
43
.26
4.0
54
.07
4.1
04
.12
4.5
8
7.1
6 C
6D
6
22,23,25,26
13,1518,20
17,19
6,9
21,24
1 O2
Ga3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
2223
24
2526
1HNMR(300MHz,C6D6)δ4.58(s,1H),4.09(q,J=7.3
Hz,4H),3.18(dp,J=9.4,6.6Hz,2H),1.52(s,6H),1.08(t,
J=7.1Hz,6H),0.83(d,J=6.5Hz,12H).
* * * *
-100102030405060708090100110120130140150160170180190200210f1(ppm)
14
.95
18
.94
24
.04
44
.29
58
.19
82
.90
12
8.0
6 C
6D
6
16
0.3
2
17
0.7
2
22,23,25,26
13,156,9
18,201,10 5,8 17,19 21,24
1 O2
Ga3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
2223
24
2526
13CNMR(75MHz,C6D6)δ170.72,160.32,82.90,58.19,
44.29,24.04,18.94,14.95.
S20
Fig38.1H–13CHSQCNMRof[GaCl(AMEiPr)2](2-Ga)
Fig39.1HNMRof[GaCl(AMEDip)2](3-Ga)
0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.6f2(ppm)
0
50
100
150
f1(ppm)
6,9 17,19 21,24 13,15 18,20
22,23,25,26
1,10
5,8
6,9
17,19
21,24
22,23,25,2613,15
18,20
1 O2
Ga3
N4
5
6
N7
8
9
10O11
Cl12
13
O14
15
O16
17
18
19
20
21
2223
24
2526
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1(ppm)
6.1312.116.086.016.002.052.121.961.992.006.12
0.8
40
.87
0.8
9
1.1
21
.14
1.1
41
.16
1.2
81
.30
1.4
21
.54
1.5
6
2.7
12
.72
2.7
32
.75
2.7
62
.77
3.2
53
.27
3.2
93
.30
3.3
13
.32
3.3
33
.35
3.3
63
.37
3.3
93
.42
3.4
43
.65
3.6
73
.70
3.7
23
.74
4.8
0
6.9
97
.01
7.0
17
.03
7.0
47
.05
7.0
67
.07
7.0
87
.16
C6
D6
7,28
18,20,21,22
10,31
39,4341,42
1,23
13,14,15,34,35,36
38,40 9 30
17,19
1
2 O3
Ga 4
N5
6
7
O8
9
10
11 12
13
1415
16
17 18
19
20 21
22
23
24O25
N26
27
28
O29
30
31
3233
34
3536
37
3839
40
4142
43
Cl44
1HNMR(300MHz,C6D6)δ7.08–6.99(m,6H),4.80(s,2H),3.70(p,J=6.7
Hz,2H),3.44–3.35(m,2H),3.33–3.25(m,2H),2.77–2.71(m,2H)1.55(d,J
=6.6Hz,6H),1.42(s,6H),1.29(d,J=6.8Hz,6H)1.14(dd,J=8.2,6.8Hz,
12H),0.87(t,J=7.1Hz,6H).
S21
Fig40.13C{1H}NMRof[GaCl(AMEDip)2](3-Ga)
Fig41.1H–1HCOSYNMRof[GaCl(AMEDip)2](3-Ga)
102030405060708090100110120130140150160170180f1(ppm)
14
.53
24
.11
24
.65
25
.17
26
.26
26
.38
27
.92
29
.02
60
.37
82
.64
12
3.2
61
24
.89
12
6.4
11
28
.06
C6
D6
14
3.9
71
45
.03
14
6.2
2
17
1.2
5
17
4.5
1
18,2220,21
10,311,2313,34
39,4315,36
14,35
9,30
17,1938,40
11,3212,37
16,33
2,24 7,286,2741,42
1
2 O3
Ga 4
N5
6
7
O8
9
10
11 12
13
1415
16
17 18
19
20 21
22
23
24O25
N26
27
28
O29
30
31
3233
34
3536
37
3839
40
4142
43
Cl44
23242526272829f1(ppm)
24
.11
24
.65
25
.17
26
.26
26
.38
27
.92
29
.02
18,2220,21 39,43
17,19 38,40
7,2841,42
13CNMR(75MHz,C6D6)δ174.51,
171.25,146.22,145.03,143.97,
126.41,124.89,123.26,82.64,60.37,
29.02,27.92,26.38,26.26,25.17,
24.65,24.11,14.53.
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
1
2
3
4
5
6
7
f1(ppm)
13,14,15,34,35,36 1,23 38,40 9
17,19
30 41,42
7,28
39,43
18,20,21,22
10,31
13,14,15,34,35,36
1,23
38,409
17,19
30
41,427,28
39,4318,20,21,22
10,31
1
2 O3
Ga 4
N5
6
7
O8
9
10
11 12
13
1415
16
17 18
19
20 21
22
23
24O25
N26
27
28
O29
30
31
3233
34
3536
37
3839
40
4142
43
Cl44
S22
Fig42.1H–13CHSQCNMRof[GaCl(AMEDip)2](3-Ga)
Fig43.1HNMRof[GaMe2(AMEDip)](4-Ga)
Fig44.13C{1H}NMRof[GaMe2(AMEDip)](4-Ga)
0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
20
40
60
80
100
120
140
160
180
200
f1(ppm)
13,14,15,34,35,36 1,23 38,40 9
17,19
30 41,42
7,28
39,43
18,20,21,22
10,31
2,246,27
11,32 16,33 12,37
14,35 15,36 13,34
1,23
9,30
17,19 38,40 41,42 7,2820,21 18,22 39,43
10,31
1
2 O3
Ga 4
N5
6
7
O8
9
10
11 12
13
1415
16
17 18
19
20 21
22
23
24O25
N26
27
28
O29
30
31
3233
34
3536
37
3839
40
4142
43
Cl44
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1(ppm)
6.293.336.436.493.212.162.121.003.280
.04
0.9
40
.96
0.9
81
.04
1.0
61
.19
1.2
2
1.4
5
3.1
73
.20
3.2
23
.24
3.2
73
.29
3.3
1
3.9
13
.93
3.9
53
.98
4.9
0
7.0
57
.05
7.1
6 C
6D
6
23,24
4
19,2016,17
22
211,12,13
21
15,18
1HNMR(300MHz,C6D6)δ7.05(m,3H),4.90(s,1H),3.94(q,J=7.1Hz,2H),
3.24(hept,J=6.8Hz,2H),1.45(s,3H),1.21(d,J=6.8Hz,6H),1.05(d,J=6.9
Hz,6H),0.96(t,J=7.1Hz,3H).
1
2
3
4
O5
N6
O7
8
Ga9
10
11
1213
14
15
16
17
18
19
20
21
22
23
24
-100102030405060708090100110120130140150160170f1(ppm)
-7.5
3
14
.59
23
.27
24
.50
24
.90
28
.11
60
.86
80
.95
12
4.3
31
26
.98
12
8.0
6 C
6D
6
14
0.9
4
14
4.2
8
17
3.5
31
73
.71
11,13 19,2016,17
15,18
10,14 2
124
2221 23,2431
8
173.5174.0f1(ppm)
17
3.5
3
17
3.7
1
3 1
21222324252627282930f1(ppm)
23
.27
24
.50
24
.90
28
.11
19,2016,17
15,184
13CNMR(75MHz,C6D6)δ173.71,
173.53,144.28,140.94,126.98,
124.33,80.95,60.86,28.11,24.90,
24.50,23.27,14.59,-7.53.
1
2
3
4
O5
N6
O7
8
Ga9
10
11
1213
14
15
16
17
18
19
20
21
22
23
24
S23
Fig45.1H–1H COSYNMRof[GaMe2(AMEDip)](4-Ga)
Fig46.1H–13C HSQCNMRof[GaMe2(AMEDip)](4-Ga)
Fig47.1HNMRof[GaMe2(AMEiPr)](5-Ga)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
1
2
3
4
5
6
7
f1(ppm)
11,12,13 2 21 15,18 4 16,17
19,20
22
23,24
11,12,13
2
21
15,18
416,17
19,20 22
23,24
1
2
3
4
O5
N6
O7
8
Ga9
10
11
1213
14
15
16
17
18
19
20
21
22
23
24
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f2(ppm)
0
20
40
60
80
100
120
140
160
180
200
f1(ppm)
11,12,13 2 21 15,18 4 16,17
19,20
22
23,24
31
10,14 8
12 11,13
2
21
15,18 16,1719,20 4
22
23,24
1
2
3
4
O5
N6
O7
8
Ga9
10
11
1213
14
15
16
17
18
19
20
21
22
23
24
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1(ppm)
6.629.603.281.102.141.00
0.1
1
0.9
50
.97
0.9
80
.99
1.0
0
1.4
9
3.3
83
.41
3.4
33
.45
3.4
73
.49
3.5
1
3.8
73
.89
3.9
23
.94
4.5
2
7.1
6 C
6D
6
14,15
1110
7
13
312
9
1HNMR(300MHz,C6D6)δ4.52(s,1H),3.91(q,J=
7.1Hz,2H),3.45(hept,J=6.6Hz,1H),1.49(s,3H),
0.99(d,J=6.6Hz,6H),0.97(t,J=7.1Hz,3H),0.11
(s,6H).
0.940.950.960.970.980.991.001.01f1(ppm)
0.9
5
0.9
7
0.9
8
0.9
9
1.0
0
1110
13
N1
2
3
4 O5
Ga6
7
O8
9
10
11
12
13
14
15
S24
Fig48.13C{1H}NMRof[GaMe2(AMEiPr)](5-Ga)
Fig49.1H–1H COSYNMRof[GaMe2(AMEiPr)](5-Ga)
Fig50.1H–13C HSQCNMRof[GaMe2(AMEiPr)](5-Ga)
-100102030405060708090100110120130140150160170f1(ppm)
-3.5
8
14
.73
22
.15
23
.57
49
.82
60
.28
79
.64
12
8.0
6 C
6D
6
17
0.4
21
71
.58
10,11
3 71312 9
14,1524
N1
2
3
4 O5
Ga6
7
O8
9
10
11
12
13
14
15
13CNMR(75MHz,C6D6)δ171.58,170.42,79.64,60.28,49.82,
23.57,22.15,14.73,-3.58.
-0.50.00.51.01.52.02.53.03.54.04.5f2(ppm)
0
1
2
3
4
5
f1(ppm)
3 12 9 7 10
11
13
14,15
3
12
9
7
101113
14,15
N1
2
3
4 O5
Ga6
7
O8
9
10
11
12
13
14
15
0.00.51.01.52.02.53.03.54.04.5f2(ppm)
-10
0
10
20
30
40
50
60
70
80
90
f1(ppm)
3 12 9 7 10
11
13
14,15
3
12
9
10,117
13
14,15
N1
2
3
4 O5
Ga6
7
O8
9
10
11
12
13
14
15
S25
D. Crystallographicdata
Complex 1-Al 2-Al 3-Al 1-Ga 2-Ga 3-Ga 4-Al
Chemicalformula C9H16Cl2AlNO2 C18H32ClAlN2O4 C36H52ClAlN2O4 C9H16Cl2GaNO2 C18H32ClGaN2O4 C36H52ClGaN2O4 C36H53AlN2O4
Fw(gmol-1) 268.11 402.88 639.22 310.85 445.62 658.49 619.49
Crystalsystem Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Tetragonal
a(Å) 9.04510(10) 12.1273(2) 8.90810(10) 9.08077(15) 12.1961(2) 8.97530(10) 21.07670(10)b(Å) 8.10630(10) 12.6240(2) 23.8108(2) 8.02118(10) 12.6013(2) 23.7494(2) 21.07670(10)c(Å) 18.2392(2) 14.5316(3) 16.8695(2) 18.3319(3) 14.5825(2) 16.86750(10) 16.37980(10)a(deg) 90 90 90 90 90 90 90b(deg) 98.3700(10) 103.938(2) 96.8650(10) 98.2836(16) 103.144(2) 96.4410(10) 90g(deg) 90 90 90 90 90 90 90V(Å3) 1321.10(3) 2159.21(7) 3552.52(7) 1321.34(3) 2182.42(6) 3572.75(5) 7276.35(8)Z 4 4 4 4 4 4 8
rcalcd(gcm-3) 1.346 1.239 1.195 1.563 1.356 1.268 1.129
m(mm-1) 1.346 2.160 1.497 6.439 3.048 2.045 0.816Reflnscollected 19678 34653 61929 44799 32986 60788 65063
Uniquereflns 2633 4257 7384 2646 4359 7039 7178
Rint 0.0292 0.0429 0.0404 0.0514 0.0240 0.0454 0.0545
R1andwR2[Alldata]
0.0255,0.0692 0.0442,0.1031 0.0440,0.1072 0.0256,0.0614 0.0315,0.0802 0.0320,0.0848 0.0402,
0.1055
