Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
261
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
3.13 Complexes of group 12 (Zn, Cd, Hg)
[C6H4CdO2] •+
chemical reduction
•+
O
Cd
O
H(2 H): 0.324
H(2 H): 0.155
ESR / 243
[C6H4CdO2] •+
chemical reduction
•+
O
THF
95Ste
O Cd
THF
95Ste
H(2 H): 0.337
H(2 H): 0.133
ESR / 243
[C6H4CdO2] •+
chemical reduction
95Ste
111,113
•+
O
THF
Cd: 0.686
H(4 H): 0.133
ESR / 243
Cd
O
[C6H5CdNO2] •+
H2N
•+
O
chemical reaction
2.0033
water, pH 6.6
111,113
Cd: 0.497
N: 0.351
H(3): 0.125
H(6): 0.055
H(5): 0.450
H(NH): 0.287
H(NH'): 0.302
14
Cd
ESR / 294
O
[C6H5NO2Zn] •+
H2N
•+
O
Zn
chemical reaction
2.00366
water, pH 6.6
14
ESR / 294
O
N: 0.354
H(3): 0.115
H(6): 0.050
H(5): 0.487
H(NH): 0.297
H(NH'): 0.313
temperature dependence
deuterated water, pH 6.6
ESR / 294
(continued)
Landolt-Börnstein
New Series II/26A2
88Pra
14
N: 0.344
H(3): 0.115
H(6): 0.050
H(5): 0.487
D(ND): 0.047
D(ND'): 0.047
88Pra
262
3.13 Complexes of group 12 (Zn, Cd, Hg)
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C6H5NO2Zn] •+ (continued)
water / ethanol 3:1
14
ESR / 294
water / ethanol 1:1
ESR / 294
water / dimethylsulfoxide 3:1
ESR / 294
[C8H8N2O2Zn2] •3+
• 3+
Zn
H3C
N
O
reduction of ligand with zinc
metal
dichloromethane
O
N
[Ref. p. 329
Ref. /
add. Ref.
N: 0.358
H(3): 0.118
H(6): 0.050
H(5): 0.492
H(NH): 0.310
H(NH'): 0.327
14
N: 0.366
H(3): 0.122
H(6): 0.053
H(5): 0.503
H(NH): 0.328
H(NH'): 0.347
14
N: 0.354
H(3): 0.121
H(6): 0.054
H(5): 0.493
H(NH): 0.303
H(NH'): 0.322
89Bes2
2.0038
14
N: < 0.01
H(3,6): 0.064
H(CH3): 0.303
ESR / 298
CH3
Zn
HMO calculations
[C10H11NO4Zn] •+
−
•+
COO
+
H3N
2.0041
water, acetate buffer, pH 3.0
H(aromatic, 1 H): 0.05
H(sidechain, 3 H): 0.44
ESR / RT
S
87Kal
O
Zn
O
H3C
[C10H12N4Zn] •3+
•3+
Zn
N
H3C N
chemical oxidation
reduction of ligand with zinc
metal
acetonitrile
N
N CH3
ESR / ENDOR / 293
2.0029
94Mat
14
N(1): 0.342
H(CH3): 0.359
H(2): 0.016
14
N(3): 0.129
H(5): 0.113
H(6): 0.306
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C11H23N2Zn] •
photolysis
263
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
91Kau
14
H
hexane
•
tBu
N
ESR / 300
Zn CH3
H
N
tBu
•+
N
O
14
ESR / 300
N: 0.485
H: 0.585
H(ZnCH3): 0.050
electrochemically generated
2.0057
THF
111,113
benzene
[C12H6CdN2O2] •+
N: 0.485
H: 0.585
H(ZnCH3): 0.050
92Boc1
Cd: 0.08–0.09
ESR / 295
Cd
O
N
HMO calculations
[C12H15NO4SZn] •2+
+
• 2+
COO−
H3N
chemical oxidation
2.0041
water, acetate buffer, pH 3.0
H(aromatic, 1 H): 0.04
H(sidechain, 3 H): 0.44
ESR / RT
H3C
S
O
Zn
O
H3C
[C12H16Br2HgN3O2] •
•
O
N
N HgBr2
N
O
chemical reaction
2.01
benzene
14
•
O
N
N: 0.756
ESR / 300
chemical reaction
2.01
benzene
14
N: 0.748
N
HgBr2
crystal structure, magnetic properties
91Kau
photolysis
14
•
tBu
N
Zn CH2CH3
H
94Mat
ESR / 300
[C12H25N2Zn] •
H
94Mat
crystal structure, magnetic properties
[C12H16Br2HgN3O2] •
N
O
87Kal
N
tBu
Landolt-Börnstein
New Series II/26A2
diethylether
ESR / 300
N: 0.491
H: 0.585
H(ZnCH3): 0.043
264
3.13 Complexes of group 12 (Zn, Cd, Hg)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C12H26N2Zn] •−
photolysis
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
91Kau
67
•
tBu
N
H
Zn(CH3)2
H
hexane
ESR / 300
N
tBu
[C13H11NO2Zn] •+
chemical oxidation
•+
HN
Zn: 0.179
N: 0.552
H(2 H): 0.552
13
C(6 C): 0.298
14
87Kal
2.0035
14
ESR / RT
N: 0.39
H(sidechain, 3 H): 0.41
H(N-H): 0.39
chemical oxidation
2.0035
water, acetate buffer, pH 5.0
O
Zn
O
H3C
[C13H11NO3Zn] •+
•+
OH
water, acetate buffer, pH 5.0
ESR / RT
HN
O
Zn
O
H3C
[C13H12N2O2Zn] •+
chemical oxidation
•+
NH2
N: 0.39
H(3): 0.028
H(6): 0.087
H(ortho, 2 H): 0.052
H(meta, 2 H): 0.027
H(sidechain, 3 H): 0.41
H(N-H): 0.39
87Kal
2.0035
14
water, acetate buffer, pH 5.0
ESR / RT
HN
87Kal
14
N: 0.39
H(sidechain, 3 H): 0.41
H(N-H): 0.39
O
Zn
O
H3C
[C13H27N2Zn] •
photolysis
91Kau
67
H
•
tBu
N
Zn iPr
H
N
tBu
diethylether
ESR / 300
Zn: 0.18
N: 0.490
H(2 H): 0.585
H(CH-iPr): 0.026
13
C(6 C): 0.29
14
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C14H10NO4Zn] •
chemical oxidation
2.0035
87Kal
COO−
14
•
HN
265
ESR / RT
N: 0.39
H(sidechain, 3 H): 0.41
H(N-H): 0.39
chemical oxidation
2.0035
water, acetate buffer, pH 5.0
O
Zn
O
H3C
[C14H15N3O2Zn] •+
•+
NH2
water, acetate buffer, pH 5.0
ESR / RT
HN
87Kal
14
N: 0.39
H(sidechain, 3 H): 0.41
H(N-H): 0.39
O
Zn
O
H2N
[C14H29N2Zn] •
photolysis
91Kau
14
H
diethylether
•
tBu
N
ESR / 300
Zn tBu
H
N: 0.508
H: 0.578
N
tBu
[C14H30N2Zn] •−
photolysis
91Kau
14
H
H
tAmyl
N
Zn(CH3)2
N
tAmyl
THF
•
N: 0.552
H: 0.552
ESR / 300
[C14H30N2Zn] •−
photolysis
91Kau
14
H
•
tBu
N
Zn(CH2CH3)2
H
N
tBu
Landolt-Börnstein
New Series II/26A2
diethylether
ESR / 300
N: 0.528
H: 0.560
266
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C14H31N2OZn] •
chemical reduction
2.01
97Rij
diethylether
14
•
tBu
N
H
ESR / 298
Zn
H
N(2 N): 0.59
H(2 H): 0.49
O
Ch3
N
tBu
[C17H25O3S2Zn] •
chemical reaction
•
tBu
toluene
S
O
H(4,5): 0.37
ESR / 293
C OC2H5
Zn
88Rak
S
O
tBu
[C18H21CdNO3] •+
•+
HO
H
N
O
•+
HO
H
N
ESR / RT
H(3): 0.0244
H(5): 0.3782
H(6): 0.0716
H(α1): 0.3412
H(α2): 0.3270
chemical reaction
2.0039
acetate buffer, pH 5
H(3): 0.0185
H(5): 0.3862
H(6): 0.0661
H(α1): 0.3512
H(α2): 0.3342
ESR / RT
O
Zn
CH3
O
[C18H27O3S2Zn] •
chemical reaction
•
tBu
O
acetate buffer, pH 5
O
[C18H21NO3Zn] •+
S
C OiPr
Zn
2.0035
Cd
CH3
O
chemical reaction
toluene
96Fer
96Fer
88Rak
H(4,5): 0.36
ESR / 293
S
tBu
[C18H38N2Zn] •−
photolysis
91Kau
14
H
•
tBu
N
Zn(tBu)2
H
diethylether
N: 0.557
H: 0.557
ESR / 300
N
tBu
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C19H29CdO3S2] •
chemical reaction
•
tBu
O
THF
S
ESR / 293
C OC4H9
Cd
267
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
88Rak
111,113
Cd: 0.78
H(4,5): 0.34
S
O
tBu
[C19H29O3S2Zn] •
chemical reaction
•
tBu
carbon tetrachloride
S
O
ESR / 293
C OC4H9
Zn
88Rak
67
Zn: 0.22
H(4,5): 0.34
S
O
tBu
[C19H30NO2S2Zn] •
chemical reaction
•
tBu
O
S
C N(C2H5)2
Zn
toluene
88Rak
H(4,5): 0.37
ESR / 293
S
O
tBu
[C20H34CdO4PS2] •
chemical reaction
•
tBu
O
S
ESR / 293
P(OiPr)2
Cd
carbon tetrachloride
88Rak
111,113
Cd: 0.80
H(4,5): 0.35
S
O
tBu
[C20H34O4PS2Zn] •
chemical reaction
•
tBu
O
O
tBu
H(4,5): 0.33
P: 0.036
31
S
P(OiPr)2
Zn
carbon tetrachloride
88Rak
ESR / 293
S
toluene
ESR / 293
H(4,5): 0.33
P: 0.036
31
THF
ESR / 293
H(4,5): 0.38
P: 0.036
31
Landolt-Börnstein
New Series II/26A2
268
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C21H22CdN2O4] •+
chemical reduction
2.0036
92Boc1
dimethylformamide
111,113
•+
O
O
ESR / 295
O
N
H
Cd: 0.63
Cd
H
O
H
HMO calculations
N
[C22H30N2Zn] •−
photolysis
91Kau
14
H3C
THF
•
oXyl
N
ESR / 300
Zn(CH3)2
H3C
N: 0.466
H(CH3): 0.672
N
oXyl
[C22H30N2Zn] •−
91Kau
photolysis
67
H
THF
•
tBu
N
ESR / 300
ZnPh2
H
N
tBu
[C24H22N4Zn] •−
Zn: 0.14
N: 0.553
H: 0.553
13
C(6 C): 0.287
14
reduction with sodium metal
THF
•
ESR / 298
N
N
Zn
N
N
95Shu
H(2,13): 0.1174
H(3,12): 0.2538
H(5,10): 0.2658
H(15,20): 0.0639
14
N(1',3'): 0.0933
14
N(2'): 0.1938
14
N(4'): 0.2691
spin density calculations
[C24H32Br6Hg3N6O4] •
chemical reaction
2.01
(HgBr2)3L2•
benzene
14
O
N
•
94Mat
N: 0.767
ESR / 300
L=
N
O
N
crystal structure, magnetic properties
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C24H33Cl2N4OZn] •
tBu
H3C
Cl2Zn O
tBu
N
dichloromethane / THF
3:1
•
H3C
N
H3CO
•+
methanol / lithium
hydroxide
ESR / 298
HO
H3CO
CH3
N
O
Cd
N
COOH
MeOD / LiOD
dimethylsulfoxide / water
ESR / 298
dimethylsulfoxide /
deuterated water
ESR / 298
dioxane / water
ESR / 298
Landolt-Börnstein
New Series II/26A2
2.00
95Gol
no hyperfine structure
97Soe
113
Cd (enriched): 0.432
N(NH2): 0.119
H(NH2): 0.100
H(NH2): 0.093
H(3): 0.196
H(4): 0.043
14
N(1): 0.061
14
113
Cd (enriched): 0.432
N(NH2): 0.119
D(ND2): 0.015
D(ND2): 0.014
H(3): 0.196
H(4): 0.043
14
N(1): 0.066
14
ESR / 298
(continued)
Ref. /
add. Ref.
chemical reduction
OCH3
H2N
g-Factor /
a-Value [mT]
ESR / 10
N
N CH3
[C25H22CdN4O8] •+
O
269
14
N(NH2): 0.125
H(NH2): 0.106
H(NH2): 0.094
H(3): 0.204
H(4): 0.041
14
N(1): 0.066
14
N(NH2): 0.125
D(ND2): 0.016
D(ND2): 0.014
H(3): 0.204
H(4): 0.041
14
N(1): 0.066
14
N(NH2): 0.117
H(NH2): 0.094
H(NH2): 0.095
H(3): 0.200
H(4): 0.045
14
N(1): 0.066
270
3.13 Complexes of group 12 (Zn, Cd, Hg)
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C25H22CdN4O8] •− (continued)
dioxane / deuterated water
14
ESR / 298
[C25H22N4O8Zn] •+
•+
H3CO
methanol / lithium
hydroxide
ESR / 298
HO
H3CO
CH3
H2N
N
O
N
COOH
[C26H24F12N4O8Zn] •
HO
F3C
•
O
CF3
O
N
toluene
97Soe
14
N(NH2): 0.108
H(NH2): 0.109
H(NH2): 0.095
H(3): 0.200
H(4): 0.046
14
N(1): 0.067
14
N(NH2): 0.108
D(ND2): 0.017
D(ND2): 0.015
H(3): 0.200
H(4): 0.046
14
N(1): 0.067
O
O
00Sak
14
N: 1.02
ESR / 298
ESR / 6
Zn
N
tBu
N(NH2): 0.117
D(ND2): 0.015
D(ND2): 0.013
H(3): 0.200
H(4): 0.045
14
N(1): 0.061
chemical reaction
O
N
O
MeOD / LiOD
ESR / 298
Zn
tBu
N
Ref. /
add. Ref.
chemical reduction
OCH3
O
[Ref. p. 329
|D / hc| = 0.0054 and
0.0094 cm–1
CF3
O
F3C
IR spectroscopy, crystal structure, magnetic susceptibility
[C26H36Br6Hg3N6O4] •
chemical reaction
2.01
(HgBr2)3L2•
benzene
14
O
N
•
94Mat
N: 0.745
ESR / 300
L=
N
O
N
crystal structure, magnetic properties
[C26H38N2Zn] •
photolysis
91Kau
14
H
•
tBu
N
Zn(oXyl)2
H
diethylether
N: 0.470
H: 0.596
ESR / 300
N
tBu
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C27H30HgNO2] • +
chemical oxidation
•+
THF
O
HgPh
271
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
86Iva
ESR / 293
H(1): 0.25
H(2): 0.50
14
N: 0.45
chemical oxidation
2.00
N
tBu
O
tBu
[C27H48ClN3OZn] •+
97Hal
dichloromethane / toluene
1:1
N
N
tBu
Zn
ESR / 77
N
Cl
O
tBu
crystal structure, UV-VIS and resonance Raman spectroscopy,
electrochemistry
[C33H16N9Zn] •
CN
N
N
N
Zn
N
N
N
N
N
electrochemical oxidation
•
2.0068
87Nyo
dichloromethane
ESR / 79
electrochemistry, UV-VIS and MCD spectroscopy
[C35H46HgNO2] •
chemical reaction
•
tBu
Hg(C6H4CH3)
ESR / 298
electrochemical oxidation
2.0055
N
O
tBu
tBu
[C36H21N9Zn] •+
•+
N
N
Zn
N
dichloromethane
ESR / 79
N
N
201
Hg: 0.21
N: 0.72
H(3): 0.31
H(7): 0.39
H(9): 0.21
toluene
14
O
tBu
89Kar
N
N
N
N
electrochemistry, UV-VIS and MCD spectroscopy
Landolt-Börnstein
New Series II/26A2
87Nyo
272
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C36H44N4Zn] • −
electrochemically generated
g = 1.9994
94Set
[Zn(OEP)] • −
butyronitrile
H(meso) = 0.273
ESR / 300
butyronitrile
ESR / 77
g⊥ = 1.989
g|| = 2.0027
a⊥ = 0.18
a|| = 0.32
data available for isotopomer (meso-13C) and other temperatures
(from 10 K to 300 K)
[C37H22N9Zn] •+
N
electrochemical oxidation
•+
py
N
N
N
Zn
N
N
N
N
2.0059
87Nyo
dichloromethane
ESR / 79
electrochemistry, UV-VIS and MCD spectroscopy
[C38H50N4Zn] •−
reduction with sodium metal
Et
N
Zn N
N
N
Et
THF
•
Et
Et
ESR / 298
Et
Et
95Shu
H(5,10): 0.3365
H(15,20): 0.0666
14
N(1',3'): 0.0966
14
N(2'): 0.1635
14
N(4'): 0.2509
Et
Et
spin density calculations
[C39H63N3O2Zn] •+
chemical oxidation
2.00
97Hal
dichloromethane / toluene 1:1
ESR / 77
N
tBu
N
O
tBu
Zn
N
tBu
O
tBu
crystal structure, UV-VIS and resonance Raman spectroscopy,
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
273
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C42H62N3O6Zn] •2+
electrochemically generated
2.0045
97Sok1
acetonitrile
H(1 H): 0.500
H(1 H): 0.054
H(2 H): 0.069
H(3 H): 0.218
14
N(1 N): 0.067
• 2+
N
O
ESR / 298
O
Zn
N
N
deuterated (d6) at * position
O
OCH3
N
O
=
*
tBu
O
crystal structure, electrochemistry, UV-VIS and resonance
Raman spectroscopy
N
[C44H13Cl8N11O14Zn] •−
O2N
R
O2N
O2N
NO2 R
N
N
Zn
N
N
R
NO2
electrochemically generated
•−
ESR / 4 or RT
R
NO2
Cl
R=
•+
Cl
Cl
electrochemistry, UV-VIS spectroscopy
chemical oxidation
Cl
Cl
97Oze
NO2
[C44H20Cl8N4Zn] • +
N
N
Zn
N
N
2
dichloromethane
NO2
Cl
Cl
H(2 H): 0.069
H(3 H): 0.218
D(1 D): 0.077
D(1 D): 0.008
14
N(1 N): 0.067
Cl
2.0117
92Gro
electrochemically generated
g = 1.999
96Kal
dichloromethane or
acetonitrile / THF 9:1
g⊥ = 2.001
g|| = 1.995
chloroform or
dichloromethane
ESR / 298
Cl
Cl
UV-VIS and IR spectroscopy
ESR / 295
(continued)
Landolt-Börnstein
New Series II/26A2
a⊥ (14N) = 0.118
a|| (14N) = 0.143
274
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C44H20Cl8N4Zn] • + (continued)
dichloromethane or
acetonitrile / THF 9:1
g = 1.999
ESR / 295
Ref. /
add. Ref.
g⊥ = 2.003
g|| = 1.991
a⊥(14N) = 0.054
a|| (14N) = 0.072
dichloromethane
2.0082
91Tun
2.0010
95Bar
ESR / 77
chemical oxidation
dichloromethane
ESR / 298
electrochemistry, UV-VIS and resonance Raman spectroscopy
[C44H20Cl8N4Zn] • +
•+
Cl
Cl
2.0048
dichloromethane
14
95Bar
N: 0.156
ESR / 298
Cl
N
Zn N
N
N
Cl
chemical oxidation
Cl
Cl
Cl
Cl
electrochemistry, UV-VIS and resonance Raman spectroscopy
[C44H20F8N4Zn] • +
chemical oxidation
•+
F
N
Zn N
N
N
F
95Bar
dichloromethane
ESR / 298
F
F
2.0034
F
F
F
F
electrochemistry, UV-VIS and resonance Raman spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
275
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H24BrnCl4N4Zn] •+
chemical oxidation
species 1: 2.0055
00Dav2
79,81
•+
Cl
chloroform
ESR / 298
Cl
N Br
N
Zn
N
N
Br = 0.830
species 2: 2.0032
chloroform
species 1: 2.0074
ESR / 77
species 2: 2.0037
Cl
Cl
•+
Cl
Br
Br
Br
Cl
N
N
Zn
N
N
Br
Br
Cl
Br
Br
Br
Cl
UV-VIS and NMR spectroscopy, electrochemistry
[C44H24BrnCl4N4Zn] •+
chemical oxidation
species 1: 2.0057
79,81
•+
Cl
Cl
chloroform
ESR / 298
N Br
Zn N
N
N
Br = 0.810
species 2: 2.0035
chloroform
species 1: 2.0076
ESR / 77
species 2: 2.0039
Cl
Cl
Cl
Br
Br
•+
Cl
Br
Br
N
Zn N
N
N
Br
Cl
Landolt-Börnstein
New Series II/26A2
Br
Br
Br
Cl
UV-VIS and NMR spectroscopy, electrochemistry
00Dav2
276
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H24BrnF4N4Zn] •+
chemical oxidation
species 1: 2.0052
00Dav1
79,81
•+
F
chloroform
ESR / 298
F
N Br
N
Zn
N
N
Br = 0.820
00Dav2
species 2: 2.0030
chloroform
species 1: 2.0080
ESR / 77
species 2: 2.0033
F
F
•+
F
Br
Br
Br
F
N
N
Zn
N
N
Br
Br
Br
F
Br
Br
F
[C44H28CdN4] • −
[Cd(TPP)] • −
UV-VIS and NMR spectroscopy, electrochemistry
electrochemically
generated
g = 1.995
94Set
Η(β) = 0.093
butyronitrile
ESR / 300
butyronitrile
ESR / 77
g⊥ = 1.980
g|| = 2.0024
a⊥ = 0.057
a|| = 0.11
temperature dependence: data available from 10 K to 300 K
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
277
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H28BrnN4Zn] •+
chemical oxidation
species 1: 2.0050
00Dav1
79,81
[Zn(TPP)Brn] •+
Br = 0.815
chloroform
•+
ESR / 298
00Dav2
species 2: 2.0028
Br
Br
Br
Br
N
N
Zn
N
N
Br
Br
chloroform
species 1: 2.0078
ESR / 77
species 2: 2.0019
Br
Br
UV-VIS and NMR spectroscopy, electrochemistry
[C44H28N4Zn] • +
[Zn(TPP)] • +
electrochemically or
chemically generated
2.0027
90Hub
dichloromethane
ESR / 200
ENDOR / 254
14
TRIPLE / 193
H(β): –0.20 MHz
H(m): 0.79 MHz
H(p): –0.93 MHz
H(o): –1.16 MHz
N: 4.20 MHz
data available for dichloromethane-THF mixture
[C44H28N4Zn] • +
chemical oxidation
[Zn(TPP)] • +
chloroform or
dichloromethane
2.0050
92Gro
2.0077
91Tun
chemical oxidation
2.0027
95Bar
dichloromethane
14
ESR / 298
UV-VIS and IR spectroscopy
electrochemically generated
dichloromethane
ESR / 77
N: 0.146
ESR / 298
electrochemistry, UV-VIS and resonance Raman spectroscopy
Landolt-Börnstein
New Series II/26A2
278
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H28N4Zn] • −
electrochemically
generated
g = 1.9986
94Set
[Zn(TPP)] • −
H(β) = 0.093
butyronitrile
ESR / 300
butyronitrile
ESR / 77
g⊥ = 1.989
g|| = 2.0034
a⊥ = 0.057
a|| = 0.11
data available for isotopomers (β-d8; meso-13C; 15N4) and
other solvents (THF, dimethylformamide); temperature
dependence data available from 10 K to 300 K
[C46H46N6O2Zn]
•+
•+
R
N
Zn
electrochemically
generated
2.0008
00DeB
acetonitrile
ESR / 298
N
2
acetonitrile
N
R
R=
ESR / 10
crystal structure, electrochemistry, UV-VIS spectroelectrochemistry, NMR spectroscopy
O CH3
[C48H36BrnN4O4Zn] •+
chemical oxidation
•+
OCH3
N Br
N
Zn
N
species 1: 2.0048
00Dav1
79,81
chloroform
ESR / 298
H3CO
2.0045
Br = 0.761
00Dav2
species 2: 2.0028
N
OCH3
H3CO
(continued)
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
279
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C48H36BrnN4O4Zn] •+ (continued)
chloroform
species 1: 2.0075
ESR / 77
species 2: 2.0029
•+
OCH3
Ref. /
add. Ref.
Br
Br
Br
H3CO
N
N
Zn
N
Br
N
Br
Br
OCH3
Br
Br
H3CO
UV-VIS and NMR spectroscopy, electrochemistry
[C48H36BrnN4O4Zn] •+
chemical oxidation
species 1: 2.0052
00Dav2
79,81
OCH3
•+
H3CO
chloroform
ESR / 298
N Br
N
Zn
N
N
Br = 0.820
species 2: 2.0030
chloroform
species 1: 2.0080
ESR / 77
species 2: 2.0033
OCH3
H3CO
OCH3
Br
H3CO
Br
Br
N
N
Zn
N
N
Br
•+
Br
Br
Br
Br
H3CO
OCH3
UV-VIS and NMR spectroscopy, electrochemistry
[C51H80N3O3Zn] •2+
electrochemically
generated
• 2+
2.0045
H(1 H): 0.586
acetonitrile
N
O
O
ESR / 298
Zn
N
deuteriert (d6) in *
position
N
D(1 D): 0.09
O
tBu
N
O
=
*
tBu
O
Landolt-Börnstein
New Series II/26A2
N
electrochemistry, UV-VIS and resonance Raman
spectroscopy
97Sok1
280
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C56H52N4Zn] • +
chemical oxidation
2.0068
92Gro
•+
chloroform or
dichloromethane
ESR / 298
N
N
Zn
N
N
UV-VIS and IR spectroscopy
chemical oxidation
2.0031
dichloromethane
14
95Bar
N: 0.175
ESR / 298
electrochemistry, UV-VIS and resonance Raman
spectroscopy
[C56H78CdN2O4] 2•
tBu
chemical reduction
2•
tBu
D = 11.0 mT
ESR / 77
O
N
89Kar
D = 19.0 mT
tBu
Cd
O
2
tBu
[C56H78N2O4Zn] 2•
tBu
chemical reduction
2•
tBu
O
N
89Kar
D = 18.8 mT
ESR / 77
D = 32.9 mT
electrochemical reduction
2.003
dichloromethane
14
tBu
Zn
O
2
tBu
[C56H80CdN2O4] •−
•−
tBu
Cd
ESR / RT
tBu
O
90Mai
N: 0.65
H: 0.21
N
tBu
O
tBu
2
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
281
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C56H80N2O4Zn] •−
electrochemical reduction
2.003
90Mai
dichloromethane
14
•−
tBu
Zn
ESR / RT
tBu
O
N: 0.70
H: 0.19
N
tBu
O
2
tBu
electrochemistry, UV-VIS spectroscopy
[C57H54N5OZn] •
chemical reaction
tBu
N O
N
N
Zn
N
N
Mes
•
toluene
ESR / 298
98Shu1
14
N: 1.199
H(o): 0.208
H(m): 0.087
Mes
Mes
[C58H52N4O7Zn] •−
chemical generation
•−
methanol
ENDOR / 230
N
N
Zn
N
N
O
O
O
O
O
O
Landolt-Börnstein
New Series II/26A2
95Kur
H(2β, 2 H): 0.119
H(3β): 0.0845
H(3β): 0.0957
H(5β, 1 H): 0.161
H(6): –0.231
H(γ, 4 H): 0.012
O
structure from molecular model calculations
282
3.13 Complexes of group 12 (Zn, Cd, Hg)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C58H52N4NaO7Zn] •
chemical generation
•
methanol
ENDOR / 250
N
N
Zn
N
N
O
O
Ref. /
add. Ref.
95Kur
23
Na: 0.106
H(2β, 2 H): 0.125
H(3β): 0.069
H(3β): 0.098
H(5β, 1 H): 0.180
H(6): –0.222
H(γ, 4 H): 0.012
O
O
O Na
O
O
[C59H54N5OZn] •
chemical reaction
tBu
N O
Mes
g-Factor /
a-Value [mT]
[Ref. p. 329
N
N
Zn
N
N
•
toluene
ESR / 298
98Shu1
14
N: 1.123
H(o): 0.224
H(m): 0.099
Mes
Mes
[C59H56N5OZn] •
chemical reaction
tBu
Mes
N
Zn N
N
N
•
N O
toluene
ESR / 298
98Shu1
14
N: 1.144
H(o): 0.216
H(m): 0.094
H(CH2): 0.099
H(CH2): 0.131
Mes
Mes
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C60H36N4Zn] •+
electrochemical oxidation
283
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
90Ren
14
•+
toluene-d8
ESR / 298
N
N
Zn
N
N
15
N4-substituted
N(4 N): 0.078
H(8 H, o-phenyl): 0.054
H(8 H, m-, p-phenyl):
0.037
15
N(4 N): 0.108
H(8 H, o-phenyl): 0.054
H(8 H, m-, p-phenyl):
0.018
electrochemistry, UV-VIS spectroscopy
[C76H92N4O4Zn] •+
air oxidation
•+
tBu OH
tBu
2.0078
88Mil
basic dichloromethane
ESR / 298
tBu
HO
N
N
Zn
N
N
tBu
tBu
OH
tBu
tBu
HO
tBu
[C82H50N8Zn2] • +
[Zn(TPP-p-TPP)] • +
electrochemistry, UV-VIS spectroscopy
electrochemically or
chemically generated
2.0027
90Hub
dichloromethane
ESR / 200
[C82H50N8Zn2] • +
[Zn(TPP-m-TPP)] • +
ENDOR / 254
14
TRIPLE / 193
H: 0.015
H: 0.022
electrochemically or
chemically generated
2.0027
N: 0.078
dichloromethane
ESR / 200
Landolt-Börnstein
New Series II/26A2
ENDOR / 254
14
TRIPLE / 193
H: –0.007
H: 0.033
H: 0.021
N: 0.075
90Hub
284
3.13 Complexes of group 12 (Zn, Cd, Hg)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C89H56N8Zn2] • +
electrochemically or
chemically generated
2.0027
90Hub
[Zn(TPP-CH2-TPP)] • +
dichloromethane
ESR / 200
[C92H116N8Zn] •−
R
•
R
R
N
N
Zn
N
14
TRIPLE / 193
H: 0.027
H: 0.041
electrochemical reduction
2.0025
N: 0.149
91Gir
1,2-dichloroethane
ESR / 298
R
N
ENDOR / 254
N
N
N
N
R
R
R
R
R = CHO(CH2)11CH3
electrochemistry
[C113H133B2N12O5Zn2]
2•
reaction with PbO2
2-methyl-THF
O
tBu
But
gx = gy = 2.00232
gz = 2.00350
99Shu
ESR / 77
O
O
O
O
ZnL
LZn
tBu
L = HB
N N
tBu
3
UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2