Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
159
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
g1 = 1.99
g2 = 1.99
g3 = 1.92
01Wan
3.9 Complexes of group 8 (Fe, Ru, Os)
[C5FeN6O] •3−
electrolysis
[Fe(CN)5(NO)] •3−
water
ESR / 77
14
N: 2.8
DFT calculations
[C5H22N7Ru] •2+
electrochemically generated
acetonitrile
N Ru(NH3)5
N
93Pop2
99,101
• 2+
H3C
2.0021
ESR / 300
[C5N6OOs] •3−
electrolysis
[Os(CN)5(NO)] •3−
acetonitrile
ESR / 3.5
Ru: 0.580
N(–H): 0.683
H(CH3): 0.723
14
N(–CH3): 0.870
H(2,6): 0.387
H(3,5): < 0.180
14
g1 = 1.99
g2 = 1.99
g3 = 1.92
01Wan
14
N: 3.5
DFT calculations
[C5N6ORu] •3−
electrolysis
[Ru(CN)5(NO)] •3−
acetonitrile
ESR / 3.5
g1 = 1.99
g2 = 1.99
g3 = 1.92
01Wan
14
N: 3.8
DFT calculations
[C6H60N24Ru4] •7+
(H3N)5Ru
Ru(NH3)5
N
C
N
C
C
N
C
N
Ru(NH3)5
(H3N)5Ru
[C7H9FeN2O5] •
O
OC
N
tBu
Fe
•
• 7+
electrochemically generated
2.012
acetonitrile
g1 = 2.003
g2 = 2.003
g3 = 2.029
ESR / 3–4
electrochemistry, UV-VIS, IR and NMR spectroscopy, UV-VIS and
IR spectroelectrochemistry
chemical reaction
2.0040
THF
57
CO
NO
Landolt-Börnstein
New Series II/26A2
Fe: 0.17
N: 1.69
14
N: 0.065
14
ESR / 293
CO
95Mos
87Bel
160
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C8H18N8Ru] •+
electrochemically generated
1.9893
93Pop2
acetonitrile
g|| = 1.965
g⊥ = 2.003
•+
N
N
ESR / 300
Ru(NH3)4
N
ESR / 110
N
[C9H7FeN6] •2−
electrochemically generated
•2
H3C N
N Fe(CN)4
2.0034
87Gat
14
dimethylsulfoxide
ESR / 298
N(1): 0.705
N(4): 0.811
H(CH3): 0.703
H(2,6): 0.475
H(3,5): 0.084
14
electrochemistry, NMR spectroscopy, UV-VIS and IR spectroelectrochemistry
[C9H7N6Ru] •2−
electrochemically generated
2.0061
87Gat
99
•2
H3C N
N Ru(CN)4
acetonitrile
ESR / 298
Ru: 0.390
Ru: 0.437
14
N(1): 0.760
14
N(4): 0.895
H(CH3): 0.624
H(2,6): 0.452
H(3,5): < 0.030
101
electrochemistry, NMR spectroscopy, UV-VIS and IR spectroelectrochemistry
[C9H8FeN6] •3−
chemical reduction
2.0032
85Eat
14
H3C N
N Fe(CN)4(H)
• 3−
methanol, high pH
ESR / 298
N(1): 0.968
H(CH2): 0.428
H(CH3): 0.09
14
N(4): 0.690
H(CH3): 0.690
HMO calculations
[C10H7FeN7] •3−
chemical reduction
2.0032
85Eat
14
• 3−
H3C N
N Fe(CN)5
methanol, high pH
ESR / 298
N(1): 0.821
H(CH2): 0.477
H(CH3): 0.102
14
N(4): 0.718
H(CH3): 0.718
HMO calculations
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
161
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C10H7N7Os] •3−
electrochemically generated
2.0157
87Gat
dimethylsulfoxide
H(CH3) ≈ 0.550
H(2,6) ≈ 0.550
•3
H3C N
N Os(CN)5
ESR / 298
electrochemistry, NMR spectroscopy, UV-VIS and IR spectroelectrochemistry
[C10H62N24Ru4] •7+
(H3N)5Ru
N
C
C
N
(H3N)5Ru
Ru(NH3)5
N
C
C
N
Ru(NH3)5
[C10H7FeN7] •3−
H3C N
N Fe(CN)5
• 3−
• 7+
electrochemically generated
2.002
dimethylformamide
3.0 mT line width
ESR / 3–4
electrochemistry, UV-VIS, IR and NMR spectroscopy, UV-VIS
and IR spectroelectrochemistry
electrochemically generated
2.0032
93Bru
aqueous CH3OHdichloromethane
H(CH3): 0.718
N(–CH3): 0.821
H(2,6): 0.477
H(3,5): 0.102
14
N(–Fe): 0.718
93Pop2
ESR / RT
[C11H19N2O2Ru] •
iPr
N
Ru(CH3)(CO) 2
N
iPr
14
photolysis
•
95Mos
toluene
95Nie
99,101
Ru: 0.245
N(2 N): 1.050
14
ESR / 298
UV-VIS and IR spectroscopy
[C12H6FeN8] •3−
electrochemically generated
1.9965
14
•3
N
N
acetonitrile
ESR / 298
Fe(CN)4
N
N
Landolt-Börnstein
New Series II/26A2
N(1,1'): 0.51
H(3,3'): 0.06
14
N(4,4'): 0.06
H(5,5'): 0.43
H(6,6'): 0.06
electrochemistry, UV-VIS spectroscopy
95Wal
162
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C12H6N8Ru] •3−
electrochemically generated
1.9934
95Wal
acetonitrile
101
•3
N
Ru: 0.514
Ru: 0.458
14
N(1,1'): 0.49
H(5,5'): 0.49
99
N
ESR / 298
Ru(CN)4
N
N
electrochemistry, UV-VIS spectroscopy
[C12H15N2O2Ru] •
photolysis
iPr
N
Ru(CH3)(CO)2
N
•
toluene
95Nie
99,101
Ru: 0.470
N(2 N): 0.662
14
ESR / 298
UV-VIS and IR spectroscopy
[C12H20N10Ru] •+
•+
chemical reduction
1.9997
ethanol
99,101
93Pop2
Ru: 0.67
N(4 N): 0.505
14
N
N
N
ESR / 300
N
N
Ru(NH3)4
N
[C12H24FeN2O5] •+
chemical reaction
2.0280
86Bal
14
[Fe(NO)2(THF)3] •+
THF
N(2 N): 0.25
ESR / 243
IR spectroscopy
[C12H32N14Ru2] •3+
(NH3)4
Ru
N
N N
N
N N
Ru
(NH3)4
• 3+
2.000
93Pop2
g|| = 2.022
g⊥ = 1.989
93Pop1
acetonitrile
2.00
93Pop1
ESR / 2.9
g1 = 1.989
g2 = 1.989
g3 = 2.022
reduction with cobaltocene in
ethanol
ethanol
ESR / 300
electrochemistry, UV-VIS and IR spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
163
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C12H64N24Ru4] •7+
electrochemically generated
2.019
95Mos
acetonitrile
5.9 mT line width
(H3N)5Ru
Ru(NH3)5
N
C
N
C
C
N
Ru(NH3)5
C
N
(H3N)5Ru
[C12H6FeN8] •3−
• 3
N
N
N
N
Fe(CN)4
• 7+
ESR / 3–4
electrochemistry, UV-VIS, IR and NMR spectroscopy,
UV-VIS and IR spectroelectrochemistry
electrochemically generated
2.0085
dimethylformamide
g|| = 2.016
g⊥ = 2.0047
ESR / RT
95Wal
ESR / 110
electrochemistry, UV-VIS spectroscopy
[C15H12FeNO4] •
chemical reaction
•
dichloromethane
Ph
N O
ESR / 293
acetonitrile
Fe(CO)3
89Li
N: 1.12
H(o,p): 0.3
H(CH): 0.3
2.0067
14
[C15H13Fe2O3S] •
•
SMe
OC Fe
2.0067
14
ESR / 293
N: 1.12
H(o,p): 0.3
H(CH): 0.3
chemical reaction
1.956
86Sch
THF
ESR / 183
Fe CO
O
electrochemistry, UV-VIS and IR spectroscopy
[C19H20FeNO4] •
chemical reaction
•
Me
Me
2.0069
14
dichloromethane / acetonitrile
N: 1.37
H: 0.42
ESR / 293
Me
N O
Me
methylchloride / acetonitrile
14
ESR / 293
Fe(CO)3
(continued)
Landolt-Börnstein
New Series II/26A2
2.0069
N: 1.375
H: 0.36
89Li
164
3.9 Complexes of group 8 (Fe, Ru, Os)
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C19H20FeNO4] • (continued)
dimethylsulfoxide / benzene
g(1) = 2.0068
g(2) = 2.0060
ESR / 293
dimethylsulfoxide / benzene /
dichloromethane /
methylchloride
ESR / 293
[Ref. p. 329
Ref. /
add. Ref.
14
N(1): 1.34
H(1): 0.33
14
N(2): 1.395
H(2): 1.23
g(1) = 2.0066
g(2) = 2.0061
14
N(1): 1.36
H(1): 0.34
14
N(2): 1.412
H(2): 1.25
[C20H22FeNO4] •
chemical reaction
•
Me
Me
dimethylsulfoxide / benzene
ESR / 293
Me
Me
N O
Me
benzene
ESR / 293
Fe(CO)3
[C22H27N2Os] •
Me
electrochemical reduction
•
Me
Me
N Me
Os
N H
Me
g(1) = 2.0069
g(2) = 2.0066
89Li
14
N(1): 1.37
H(1): 0.4
14
N(2): 1.39
H(2): 1.27
g(1) = 2.0067
g(2) = 2.0064
14
N(1): 1.35
H(1): 0.33
14
N(2): 1.38
H(2): 1.23
1.981
94Kai
189
acetonitrile
ESR / 295
Me
Os: 2.63
N: 0.51
H(4,4'): 0.35
H(5,5'): 0.35
H(Os-H): 0.35
14
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C23H34N4O13P4Ru2] •+
chemical reaction
Et
N
P(OMe)2
CO
CO
Ru CO
OC Ru
OC
N (MeO) P
P(OMe)2
2
C
N
Et
C
N
(MeO)2P
N
C
C
N
[C24H18N12Ru] • +
•+
N
N
•+
165
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.00184
92Bel
14
dichloromethane
ESR / 300
N(1 N): 0.117
N(2 N): 0.172
14
N(1 N): 0.249
31
P(1 P): 0.430
31
P(1 P): 0.441
14
electrochemistry, UV-VIS, NIR and IR spectroscopy
electrochemically
generated
1.9964
90Kai4
1.9982
90Kai4
1.9977
90Kai4
1.9983
90Kai4
acetonitrile
Ru
ESR / 300
3
N
N
HMO calculations
[C24H18N12Ru] • +
•+
N
electrochemically
generated
acetonitrile
N
ESR / 300
Ru
3
N
N
HMO calculations
[C24H18N12Ru] • +
•+
N
electrochemically
generated
acetonitrile
N
Ru
ESR / 300
3
N
N
HMO calculations
[C24H18N12Ru] • +
•+
N
N
N
N
electrochemically
generated
acetonitrile
Ru
ESR / 300
3
HMO calculations
Landolt-Börnstein
New Series II/26A2
166
3.9 Complexes of group 8 (Fe, Ru, Os)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C27H21N4O3Ru] •
chemical reaction
H3C
O
O
O
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.0023
93Wal
99,101
•
acetonitrile
Ru(bpy)2
ESR / 300
Ru: 0.225
H(CH3): 0.588
H(CH): < 0.05
dichloromethane
ESR / 113
g1 = 2.0210
g2 = 2.0032
g3 = 1.9851
electrochemistry
[C27H25N7ORu] •+
(H3C)2N
electrochemically
generated
•+
O
1.9992
87Ern
acetonitrile
Ru(bpy)2
N
ESR / 298
N
electrochemistry, UV-VIS spectroscopy, NMR
[C27H29FeNO11] •−
O
O−
chemical oxidation
O O
−
Fe
O
O
O
H2N
[C28H22N8Ru]
90Kai4
1.9973
90Kai4
3
−
O
O
O
•+
•+
N
N
1.9908
ESR / 77
O
−
85Zwe
water
• 4−
−
2.34
electrochemically
generated
acetonitrile
Ru(bpy)2
ESR / 300
N
N
HMO calculations
[C28H22N8Ru] • +
•+
N
acetonitrile
N
Ru(bpy)2
N
electrochemically
generated
14
N (4 N): 0.27
H (2 H): 0.23
ESR / 300
HMO calculations
N
ESR / 298
1.9975
85Ern
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
167
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C28H22N8Ru] • +
electrochemically
generated
1.9910
90Kai4
1.9942
90Kai4
1.9977
89Bes2
•+
N
acetonitrile
N
Ru(bpy)2
ESR / 300
N
N
HMO calculations
[C28H22N8Ru] • +
electrochemically
generated
•+
N
N
N
N
acetonitrile
Ru(bpy)2
ESR / 300
HMO calculations
[C28H24N6O2Ru2] •3+
H3C
O
chemical reduction
N
Ru(bpy))2
acetone
• 3+
Ru(bpy)2
N
O
ESR / 298
ESR / 3.8
CH3
g1 = 1.9645
g2 = 2.0027
g3 = 2.0252
HMO calculations
[C29H32N2O2RuSn] •−
chemical reduction
•
N
Ru(CO)2(CH 3)(SnPh 3)
1.9986
97Aar
99
THF
ESR / 293
N
Ru: 0.39
Ru: 0.43
117
Sn: ~ 370
119
Sn: ~ 37
14
N: 0.795
H(imine): 0.362
H(CH(CH3)2): 0.269
H(Ru-CH3): 0.068
101
UV-VIS and IR spectroelectrochemistry, electrochemistry,
NMR spectroscopy
[C29H34N2O2PRu] •
iPr
N
Ru(PPh3)(CH3)(CO)2
N
iPr
Landolt-Börnstein
New Series II/26A2
95Nie
photolysis
•
toluene
99,101
Ru: 0.202
P: 7.267
14
N(2 N): 0.774
31
ESR / 298
UV-VIS and IR spectroscopy
168
3.9 Complexes of group 8 (Fe, Ru, Os)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C29H38N4O13P4Ru2] •+
chemical reaction
•+
Et
N
N
N
C
C
C
C
N
(MeO)2P
P(OMe)2
(CO)2Ru
Ru(CO)3
(MeO)2P
N
Et
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.00220
92Bel
14
dichloromethane
ESR / ENDOR / 300
P(OMe)2
N(1 N): 0.054
N(1 N): 0.117
14
N(2 N): 0.133
31
P(1 P): 0.189
31
P(2 P): 0.205
H(2 H): 0.022
H(2 H): 0.260
14
electrochemistry, UV-VIS, NIR and IR spectroscopy
N
[C30H24N6Os] •+
electrochemically generated
[Os(bpy)3] •+
dimethylformamide
1.989
85Mor2
ESR / 233
dimethylformamide
1.998
ESR / 133
charge = 0
dimethylformamide
1.990
ESR / 233
dimethylformamide
2.001
ESR / 133
solid
1.990
ESR / 133
dimethylformamide
charge = 1−
1.968
ESR / 133
[C30H24N6Ru] • +
electrochemically generated
•+
N
1.9961
90Kai4
acetonitrile
ESR / 300
Ru
N
3
HMO calculations
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
169
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C30H24N8Ru] • +
electrochemically generated
1.9978
90Kai4
acetonitrile
1.9983
93Kre
ESR / 300
99
•+
N
N
Ru: 0.77
Ru: 0.86
14
N(1 N): 0.73
101
Ru(bpy)2
N
N
HMO calculations
α1-[C30H24N10Ru] •+
electrochemically generated
•+
N N py
1.9858
acetonitrile
93Kre
96Hei1
ESR / 180
N
Ru(bpy)
N
N N
py
electrochemistry, UV-VIS and IR spectroscopy, NMR
α2-[C30H24N10Ru] •+
electrochemically generated
•+
py
py
N
N
1.998
96Hei1
acetonitrile
ESR / 298
N
Ru(bpy)
N
N
N
electrochemistry, UV-VIS and NMR spectroscopy, temperature
dependent ESR data
β-[C30H24N10Ru] •+
N N py
•+
1.9978
acetonitrile
ESR / 298
N
py
electrochemically generated
Ru(bpy)
N
N
N
electrochemistry, UV-VIS, IR and NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
93Kre
96Hei1
170
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C30H24N12Ru] • +
electrochemically generated
1.9966
90Kai4
1.9978
93Kre
•+
acetonitrile
N
N
Ru
ESR / 300
N
3
N
HMO calculations
fac-[C30H24N12Ru] •+
electrochemically generated
•+
N N
py
Ru
N
N
ESR / 298
N
N
py
acetonitrile
N
N
N
py
electrochemistry, UV-VIS and IR spectroscopy, NMR
mer-[C30H24N12Ru] •+
electrochemically generated
•+
py
py
N
N
93Kre
acetonitrile
ESR / 298
N
N
Ru
N
N
1.9985
N
N
N
py
electrochemistry, UV-VIS and IR spectroscopy, NMR
[C30H28N8Ru] •3+
(bpy)2Ru
N
N
H3C N
electrochemically generated
•3+
N CH3
acetonitrile
1.9963
90Kai3
94Mat
ESR / 298
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C30H30N2O2PRu] •
photolysis
•
iPr
N
Ru(PPh3)(CH3)(CO)2
N
toluene
171
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
95Nie
99,101
Ru: 0.303
P: 5.211
14
N(2 N): 0.433
H(imine): 0.120
31
ESR / 298
UV-VIS and IR spectroscopy
[C31H22ClN8O3ReRu] •+
Ru(bpy)2
N
N
N
•+
•+
N
Mo(CO)4
Ru(bpy)2
•+
1.9964
1,2-dichloroethane
14
N N
CH3
1.9990
THF
101
electrochemically generated
acetonitrile
ESR / 298
Ru(bpy)2
N
Et
N
Landolt-Börnstein
New Series II/26A2
00Hor
Ru: 0.53
Ru: 0.47
14
N(5): 0.80
electrochemistry, NMR and IR spectroscopy, UV-VIS and IR
spectroelectrochemistry
• 3+
N
N: 0.24
electrochemically generated
ESR / 298
N
91Mat1
99
[C32H32N8Ru] •3+
Et
electrochemically generated
N
N
Re: 1.05
also electrochemistry, UV-VIS spectroscopy
O
O
185,187
ESR / RT
[C32H26N8O2Ru] •+
H3C
1,2-dichloroethane
91Mat1
electrochemistry, UV-VIS spectroscopy
[C32H22MoN8O4Ru] •+
N
1.9953
ESR / RT
N
Re(CO)3Cl
Ru(bpy)2
N
N
electrochemically generated
electrochemistry
1.9834
90Kai3
172
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C32H36FeN4] •−
electrochemically generated
2.006
98Ber2
benzonitrile
•
ESR / 140
N
Fe N
N
N
electrochemistry, UV-VIS spectroscopy
[C33H20N6O8Ru] •−
electrochemically generated
COO−
2.0048
90Sch
acetonitrile
•
ESR / 300
N
O
−
OOC
adsorbed on Al2O3
Ru(bpy)2
O
HN
ESR / 300
HOOC
g1 = 2.0210
g2 = 2.0032
g3 = 1.9851
electrochemistry, UV-VIS spectroscopy
[C33H28N8O2Ru] • +
electrochemically generated
N
H3C
N
H3C
ESR / 298
NH
N
H3C
O
Ru(bpy)2
electrochemistry, UV-VIS spectroscopy
[C33H32N4O5Ru] • +
Me
92Sch2
acetonitrile
•+
O
2.0016
CO
N
Ru N
N
N
Me
Me
chemical oxidation with Br2
•+
Me
COOCH3
2.003
86Mor
dichloromethane
ESR / 77
COOCH3
NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
173
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C34H25FeO4P2] •
irradiation
2.008
95Mey
dichloromethane
31
Ph2
P
Fe(CO)Cp
P
Ph2
O
O
O
•
ESR / 298
IR spectroscopy, electrochemistry
[C34H27FeO3P2] •
Ph2
P
Fe(CO)Cp
P
Ph2
O
O
•
2.004
dichloromethane
31
95Mey
P: 0.93 (2P)
H: 0.29 (2H)
IR spectroscopy, electrochemistry
•
Ph2
P
Fe(CO)2Cp
O
irradiation
ESR / 298
[C35H25FeO5P2] •
O
P: 0.87 (2P)
irradiation
2.008
dichloromethane
31
95Mey
P(1): 0.97
P(2): 0.39
31
ESR / 298
PPh2
O
IR spectroscopy, electrochemistry
[C35H27FeO4P2] •
Ph2
P
Fe(CO)2Cp
O
•
irradiation
2.004
dichloromethane
31
P(1): 1.05
P(2): 0.44
H(1): 0.33
H(2): 0.27
31
ESR / 298
PPh2
O
95Mey
IR spectroscopy, electrochemistry
[C35H28FeNO3P2] •
Ph2
P
Fe(CO)Cp
P
Ph2
O
H3C N
O
•
Et
Et
Et
Landolt-Börnstein
New Series II/26A2
95Mey
P(1): 0.87
P(2): 0.86
IR spectroscopy, electrochemistry
benzonitrile
g1 = 2.12
g2 = 2.07
g3 = 2.02
96Van
ESR / 77
Et
Et
Et
31
electrochemically generated
N
Fe N
N
N
Et
dichloromethane
ESR / 298
•+
Cl
2.008
31
[C35H43ClFeN4] •+
Et
irradiation
electrochemistry, magnetic susceptibility, UV-VIS and Mössbauer
spectroscopy
174
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C35H43FeN5O] • +
electrochemically generated
g1 = 2.02
g2 = 2.00
g3 = 1.98
97Aar
•+
Et
Et
NO
Et
N
Fe N
N
N
Et
ESR / 120
Et
Et
Et
crystal structure, electrochemistry, UV-VIS, IR and NMR
spectroscopy
Et
[C36H32N6O4Ru] • +
electrochemically generated
•
O COEt
benzonitrile
+
1.997
87Gas
dimethylformamide
ESR / 300
N
ESR / 77
Ru(bpy)2
N
g|| = 1.986
g⊥ = 2.004
O COEt
electrochemistry, UV-VIS spectroscopy
[C36H32N6O4Ru] • −
electrochemically generated
•
O COEt
−
dimethylformamide
g|| = 1.9933
g⊥ = 2.0032
87Gas
ESR / 77
N
Ru(bpy)2
N
O COEt
electrochemistry, UV-VIS spectroscopy
[C36H43ClFeN5O2] • −
Et
Et
•−
Cl
Et
N
Fe N
N
N
Et
Et
O2N
chemical reduction
5.63
THF
2.00
92Yam
ESR / 77
Et
Et
Et
NMR and UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
175
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C37H40N4O5Ru] • +
chemical oxidation with
Br2
2.003
86Mor
Et
Me
•+
CO
Me
dichloromethane
N
Ru N
N
N
Et
COOCH3
Me
ESR silent at room
temperature
ESR / 77
COOCH3
Me
NMR spectroscopy
[C38H26N8Ru] •+
•+
N
N
N
N
electrochemically
generated
dichloromethane
Ru(bpy)2
ESR / 293
2.00336
99Fee
14
N(9,14): 0.48
H(10,13): 0.13
14
N(4,5): 0.07
H: 0.07
electrochemistry, UV-VIS spectroscopy and
spectroelectrochemistry
electrochemically
generated
dichloromethane
2.00336
93Fee
14
N(9,14): 0.48
H(10,13): 0.13
ESR / 293
electrochemistry, UV-VIS spectroscopy, NMR
[C39H31N8OPRu] •+
chemical reaction
•+
N
N
N
N
N
2.003
powder
00Shi
ESR / 298
N
ESR / 77
1.999
Ru
CO
N
N
PPh3
Landolt-Börnstein
New Series II/26A2
00Gho
crystal structure, electrochemistry, UV-VIS and IR
spectroscopy, magnetic measurements
176
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C39H66N4O13P4Ru2] •+
chemical reaction
2.00199
92Bel
14
•+
Et
N
ESR / 300
(iPrO)2P
N
C
C
N
dichloromethane
P(OiPr)2
CO
CO
Ru CO
OC Ru
OC
N (iPrO) P
P(OiPr)2
2
C
N
Et
C
N
N(1 N): 0.117
N(2 N): 0.172
14
N(1 N): 0.251
31
P(1 P): 0.523
31
P(1 P): 0.536
14
electrochemistry, UV-VIS, NIR and IR spectroscopy
[C40H30N8Ru] •+
•+
electrochemically
generated
2.00339
93Fee
14
N(9,14): 0.47
dichloromethane
H3C
N
N
Ru(bpy)2
H3C
N
ESR / 293
N
electrochemistry, UV-VIS spectroscopy, NMR
[C41H48FeN4] •+
electrochemically
generated
•+
benzonitrile
Et
Et
Et
Et
Et
Et
crystal structure, electrochemistry, magnetic susceptibility,
UV-VIS and Mössbauer spectroscopy
Et
[C42H26N8Os] •+
•+
N
N
N
N
96Van
ESR / 77
Et
N
Fe N
N
N
g1 = 2.17
g2 = 2.04
g3 = 2.01
electrochemically
generated
2.00395
99Fee
14
N(9,14): 0.45
acetonitrile
Os(phen)2
ESR / 293
electrochemistry, UV-VIS spectroscopy and
spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
177
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C43H18Cl8FeN4O3] • +
chemical oxidation
g1 = 2.17
g2 = 2.17
g3 = 1.99
97Jay
•+
butyronitrile
Cl
Cl
O
O
N
N C O
Fe
Cl
Cl
N
N
Cl
Cl
Cl
ESR / 4.2
Cl
crystal structure, electrochemistry, NMR, UV-VIS and
resonance Raman spectroscopy
[C44H8F20FeN4O] • +
chemical oxidation
•+
F
F
NO
Fe N
N
N
F
F
F
F
F
F
F
F
UV-VIS and NMR spectroscopy
[C44H16Cl12FeN4O] • +
chemical oxidation
•+
Cl
Cl
Cl
Cl
Cl
NO
Fe N
N
N
Cl
dichloromethane
ESR / 14
F
F
F
94Fuj
F
F
F
F
F
F
F
2.0
ESR / 14
E / D = 0.040
chemical oxidation
geff|| ≈ 2
geff⊥ ≈ 4
96Fuj
Cl
Cl
Cl
dichloromethane / methanol
5:1
g1 = 4.14
g2 = 3.66
g3 = 2.00
Cl
Cl
Cl
[C44H20Cl6FeN6O5] • +
•+
Cl
NO
Fe N
N
N
Cl
ESR / 10
Cl
Cl
Cl
Cl
dichloromethane / methanol
96Jay
NO2
O2N
NMR, UV-VIS, IR and resonance Raman spectroscopy
Landolt-Börnstein
New Series II/26A2
178
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H20Cl7FeN5O3] • +
chemical oxidation
geff|| ≈ 2
geff⊥ ≈ 4
96Jay
•+
Cl
NO
Fe N
N
N
Cl
ESR / 10
Cl
Cl
Cl
Cl
dichloromethane / methanol
Cl
O2N
NMR, UV-VIS, IR and resonance Raman spectroscopy
[C44H20Cl8FeN4O] • +
•+
Cl
Cl
Cl
geffx = 4.26
geffy = 3.62
dichloromethane / methanol 6:1 geff = 1.98
z
chemical oxidation
ESR / 2.7–30
Cl
NO N
Fe
N
N
92Man
Cl
Cl
Cl
Cl
NMR, UV-VIS, resonance Raman and Mössbauer spectroscopy
[C44H20Cl8FeN4O] • +
•+
Cl
NO
N
Fe
N
N
Cl
ESR / 20
Cl
Cl
g1 = 4.23
g2 = 3.65
dichloromethane / methanol 5:1 g = 2.00
3
chemical oxidation
96Fuj
E / D = 0.048
Cl
Cl
Cl
Cl
[C44H28FFeN4O] •
chemical oxidation
[Fe(O)(TPP)F] •
dichloromethane
g1 = 4.2
g2 = 3.9
g3 = 3.5
88Hic
ESR / 5
electrochemistry, NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
179
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H30FeN4O12S4] • 3−
chemical reaction
2
97Jim
•3
SO3
solid state
ESR / 423
O3S
N
N
Fe N
N
SO3
SO3
electrochemistry, NMR spectroscopy
[C44H36FeN8O] •+
•+
N
CH3
N
NO N
Fe
N
N
H3C
N
electrochemically
generated
2 (broad signal)
92Rod
water, pH = 9.1
CH3
ESR / 120
N
H3C
electrochemistry, NMR and resonance Raman spectroscopy
[C44H37FeN8O2] •
•
N
CH3
N
NO N
Fe
N
N
H3C
N
OH
electrochemically
generated
2.44 (broad signal)
92Rod
water, pH = 12.1
CH3
ESR / 120
N
H3C
electrochemistry, NMR and resonance Raman spectroscopy
Landolt-Börnstein
New Series II/26A2
180
3.9 Complexes of group 8 (Fe, Ru, Os)
Substance
[C44H55FeN8O] •
N
Et
CH3
N
Et
•
Et
N
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
chemical reaction
2.53
95Mor
1-methylimidazole
2.28
ESR / 77
1.66
Et
N
Fe N
N
N
Et
[Ref. p. 329
Et
O
Et
Et
N
H3C
NMR and UV-VIS spectroscopy
[C45H53FeN6O] •
electrochemically generated
•
Et
N
Et
Et
Et
1.981
93Taj
dimethylformamide / pyridine
ESR / 253
Et
dimethylformamide / pyridine
N
Et
Fe N
N
O
N
N Et Et
ESR / 77
g|| = 1.935
g⊥ = 2.001
electrochemistry, UV-VIS spectroelectrochemistry
[C45H70N4O13P4Ru2] •+
chemical reaction
•+
Et
N
N
N
C
C
C
C
(iPrO)2P
P(OiPr)2
(CO)2Ru
N
(iPrO)2P
Ru(CO)3
N
Et
92Bel
2.00222
14
dichloromethane
ESR / ENDOR / 300
P(OiPr)2
N(1 N): 0.055
N(1 N): 0.123
14
N(2 N): 0.131
31
P(1 P): 0.198
31
P(2 P): 0.203
H(2 H): 0.018
H(2 H): 0.259
14
electrochemistry, UV-VIS, NIR and IR spectroscopy
N
[C46H44GeN2O2RuSn] •−
reduction with 1 % Na (Hg)
97Aar
1.9960
99
•
ESR / 293
N
Ru(CO)2(GePh3)(SnPh3)
N
THF
Ru: 5.7
Ru: 6.4
117
Sn: 317
119
Sn: 332
14
N: 8.2
H(imine): 3.55
H(CH(CH3)2): 3.25
101
UV-VIS and IR spectroelectrochemistry, electrochemistry,
NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
[C46H44N2O2Pb2Ru]
•−
181
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
reduction with 1% Na (Hg)
1.9919
97Aar
207
•
THF
N
ESR / 293
Ru(CO)2(PbPh3)2
Pb: ~57
N: ~0.75
H(imine): ~0.4
H(CH(CH3)2): ~0.33
14
N
UV-VIS and IR spectroelectrochemistry, electrochemistry,
NMR spectroscopy
•+
[C46H46FeN6O4]
•+
R
N
electrochemically generated
1.977
acetonitrile
gx = 1.996
gy = 1.975
gz = 1.961
ESR / 253
N
Fe
00DeB
2
N
R
R=
O CH3
crystal structure, electrochemistry, UV-VIS spectroelectrochemistry, NMR and Mössbauer spectroscopy
[C46H53FeN6O] •
•
Et
Et
Et
2.31
pyridine
1.79
95Mor
ESR / 77
N
Et
N
Fe N
N
N
Et
chemical reaction
N
Et
O
Et
Et
NMR and UV-VIS spectroscopy
[C47H38BrN4OOsP2]
•−
•
N
N
chemical reaction
2.001
polycrystalline solid
1.971
ESR / 298
Os(CO)(PPh3)2Br
N
N
crystal structure, electrochemistry, NMR
Landolt-Börnstein
New Series II/26A2
00Pra
182
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C47H38ClN4OP2Ru] •
chemical reaction
2.001
00Gho
•
powder
N
N
ESR / 298
Ru(PPh3)2(CO)Cl
ESR / 77
N
N
electrochemistry, UV-VIS and IR spectroscopy, magnetic
measurements
[C47H39N4OP2Ru] •
chemical reaction
•
2.002
powder
N
N
2.001
00Gho
00Shi
ESR / 298
Ru(PPh3)2(CO)H
ESR / 77
N
N
2.003
electrochemistry, UV-VIS and IR spectroscopy, magnetic
measurements
[C48H24FeN8] • −
chemical reduction
•−
NC
THF
gx = 2.032
gy = 1.86
gz = 2.0
92Yam
ESR / 77
CN
N
N
Fe
N
N
NC
CN
NMR and UV-VIS spectroscopy
[C48H24Cl12FeN4O] • +
CH3
Cl
H3C
Cl
•+
Cl
Cl
Cl
chemical oxidation
96Fuj
Cl
NO
Fe N
N
N
Cl
dichloromethane /
methanol 5:1
g1 = 3.6
g2 = 1.98
H3C Cl
ESR / 4
Cl
CH3
Cl
Cl
Cl
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
183
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H28Cl8FeN4O] • +
chemical oxidation
g1 = 3.6
g2 = 1.98
96Fuj
•+
Cl
CH3
Cl
CH3
NO
Fe N
N
N
Cl
H3C
Cl
Cl
dichloromethane / methanol
5:1
Cl
ESR / 10
Cl
H3C Cl
[C48H32FeN20] 2•
chemical synthesis
spin crossover, ESR
of CuII and MnII
doped systems
2•
NC
CN
C
N
CN
N
N
H2N N N
N
Fe
N
NC
N
C
NC
CN
N NH2
N
N
N
crystal structure, magnetic measurements, IR and Mössbauer
spectroscopy
[C48H32Cl4FeN4O] • +
chemical oxidation
•+
Cl
CH3
Cl
96Kun
CH3
NO
Fe N
N
N
dichloromethane / methanol
5:1
g1 = 4.31
g2 = 3.62
g3 = 1.99
96Fuj
ESR / 14
E / D = 0.057
electrochemically generated
1.9890
90Kai4
acetonitrile
99,101
91Mat1
Cl
H3C
H3C
Cl
[C48H38N12Ru2] •3+
Ru(bpy)2
N
N
N
N
Ru(bpy)2
Landolt-Börnstein
New Series II/26A2
• 3+
Ru: 0.27
N: 0.274
H(5,5'): 0.44
14
ESR / 300
HMO calculations
184
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H38Cl2N3OP2Ru] •
chemical reaction
2.000
00Gho
•
N
N
ESR / 298
Ru(PPh3)2(CO)Cl
N
ESR / 77
Cl
electrochemistry, UV-VIS and IR spectroscopy, magnetic
measurements
[C48H39BrN3OOsP2]
•−
•
N
N
powder
2.000
chemical reaction
1.998
polycrystalline solid
1.966
00Pra
ESR / 298
Os(CO)(PPh3)2Br
N
crystal structure, electrochemistry, NMR
[C48H39ClN3OP2Ru] •
chemical reaction
•
N
N
2.000
00Gho
powder
ESR / 298
Ru(PPh3)2(CO)Cl
ESR / 77
N
2.001
crystal structure, electrochemistry, UV-VIS and IR spectroscopy,
magnetic measurements
[C48H39ClN3OP2Ru] •
chemical reaction
•
N
N
2.000
00Gho
powder
00Shi
ESR / 298
Ru(PPh3)2(CO)H
N
ESR / 77
2.003
Cl
electrochemistry, UV-VIS and IR spectroscopy, magnetic
measurements
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
185
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H57FeN6O] •
chemical reaction
2.31
95Mor
4-methylpyridine
1.75
•
CH3
ESR / 77
Et
N
Et
Et
N
Fe N
N
N
Et
Et
Et
O
Et
N
Et
NMR and UV-VIS spectroscopy
CH3
[C49H37N8O3PReRu] •2+
Ru(bpy)2
N
N
N
• 2+
1.9944
1,2-dichloroethane
185,187
91Mat1
Re: 1.9
P: 1.7
ESR / RT
31
electrochemically generated
1.9984
87Kai1
1.9984
90Kai4
N
Re(CO)3PPh3
[C50H40N12Ru2] •3+
Ru(bpy)2
N
• 3+
acetonitrile
ESR / RT
N
N
N
Ru(bpy)2
[C50H49N12Ru2] •3+
Ru(bpy)2
N
electrochemically generated
N
N
electrochemically generated
• 3+
acetonitrile
ESR / 300
N
Ru(bpy)2
HMO calculations
Landolt-Börnstein
New Series II/26A2
186
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C50H57FeN6O3] •
chemical reaction
2.20
95Mor
4-acetylpyridine
1.90
O
•
CH3
ESR / 77
Et
Et
N
Et
N
Fe N
N
N
Et
Et
O
Et
N
H3C
Et
Et
O
NMR and UV-VIS spectroscopy
[C50H61FeN6O] •
•
CH3
CH3
Et
Et
N
Et
N
2.31
3,4-dimethylpyridine
1.73
95Mor
ESR / 77
Et
N
Fe N
N
N
Et
chemical reaction
Et
O
Et
Et
H3C
NMR and UV-VIS spectroscopy
CH3
[C52H38N10O2Ru2] •3+
electrochemically generated
• 3+
(bpy)2Ru
N
O
O
Ru(bpy)2
N
2.0112
87Ern
2.0098
87Ern
g1 = 2.032
g2 = 2.032
g3 = 1.996
89Ern
acetonitrile
ESR / 298
1,2-dichloroethane
ESR / 298
acetone
ESR / 4
electrochemistry, UV-VIS spectroscopy, NMR
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
187
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C52H40N14Os2] •3+
electrochemically generated
1.9989
89Koh
chemical reduction
1.9865
85Kai
acetone
99,101
•3+
Os(bpy)2
ESR / 3.8
N
N N
N
acetonitrile
N N
Os(bpy)2
[C52H40N14Ru2] •3+
•3+
(bpy)2
Ru
N
N N
N
ESR / 3.8
Ru: 0.45
N: 0.55
14
N: 0.55
(coordinating)
chemical reduction
1.9980
acetone
99,101
14
N N
Ru
(bpy)2
90Kai4
Ru: 0.435
N(4 N): 0.569
14
ESR / 300
HMO calculations
acetonitrile
1.9980
93Pop1
g1 = 3.6
g2 = 1.98
96Fuj
1.9896
90Kai4
2.0256
86Bal
ESR / 3.8
[C52H40Cl4FeN4O] • +
•+
Cl
CH3
CH3
H3C
Cl
chemical oxidation
H3C
NO
Fe N
N
N
CH3
Cl
CH3
ESR / 4
H3C
H3C Cl
[C54H42N12Ru2] •3+
electrochemically generated
• 3+
Ru(bpy)2
N
dichloromethane / methanol
5:1
N
acetonitrile
ESR / 300
N
N
Ru(bpy)2
[C54H45FeN2O2P3] •+
[Fe(PPh3)3(NO)2] •+
HMO calculations
chemical reaction
14
acetonitrile / benzonitrile
ESR / 263
IR spectroscopy
Landolt-Börnstein
New Series II/26A2
N(2 N): 0.3
P: 5.25
31
188
3.9 Complexes of group 8 (Fe, Ru, Os)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C54H45FeN2O5P3] •+
chemical reaction
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.0268
86Bal
14
[Fe[P(OPh)3]3(NO)2] •+
THF
N(2 N): 0.32
P: 10.2
31
ESR / 243
IR spectroscopy
[C55H50FeN4O3] • +
chemical oxidation
•+
toluene
g1 = 2.18
g2 = 2.20
g3 = 1.99
97Jay
ESR / 1.8
NO N
Fe
N
N
O
C O
electrochemistry, NMR, UV-VIS and resonance Raman
spectroscopy
[C55H53NO2P4Ru] •+
tBu
Ph2P
N
•+
O
chemical reaction
2.006
dichloromethane
H: 0.079
14
N: 1.340
ESR / 293
84Smi
PPh2
Ru
Ph2P
PPh2
CO
[C56H44Cl8FeN4O] • +
chemical oxidation
•+
Cl
Cl
Cl
Cl
dichloromethane / methanol
6:1
geffx = 4.2
geffy = 3.7
geffz = 1.99
92Man
93Och
Cl
ESR / 10
NO N
Fe
N
N
Cl
Cl
Cl
NMR, UV-VIS, resonance Raman and Mössbauer
spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
189
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C56H52FeN4O] • +
chemical oxidation
geff = 3.5 broad
geff = 2 intense
96Ayo
•+
benzonitrile
ESR / 120
NO
Fe N
N
N
gx = 3.48
gy = 3.02
gz = 1.995
Mössbauer and resonance Raman spectroscopy
chemical oxidation
dichloromethane /
methanol 6:1
geffx = 4.47
geffy = 3.50
geffz = 1.98
92Man
ESR / 2.7–30
NMR, UV-VIS, resonance Raman and Mössbauer
spectroscopy
chemical oxidation
dichloromethane /
methanol 5:1
[C56H52FeN4O13] • +
•+
R
g1 = 4.36
g2 = 3.58
g3 = 1.99
ESR / 14
E / D = 0.065
chemical oxidation
geffx = 3.71
geffy = 3.71
geffz = 1.99
dichloromethane /
methanol 6:1
96Fuj
92Man
R
ESR / 2.7–30
R
R
R
NO N
Fe
N
N
R
R
R
R
R
R
R
R = OCH3
NMR, UV-VIS, resonance Raman and Mössbauer
spectroscopy
[C56H54BrFeN4O] •
chemical oxidation
[Fe(O)(TMP)Br] •
butyronitrile
gx = 3.643
gy = 4.35
gz = 1.98
ESR / 194
Mössbauer and UV-VIS spectroscopy, EXAFS
Landolt-Börnstein
New Series II/26A2
00Wol
190
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C56H54ClFeN4O] •
chemical oxidation
00Wol
[Fe(O)(TMP)Cl] •
butyronitrile
gx = 3.780
gy = 4.23
gz = 1.999
ESR / 194
Mössbauer and UV-VIS spectroscopy, EXAFS
[C56H54FeN4O] •+
chemical oxidation
[Fe(O)(TMP)] •+
dichloromethane or toluene
gx = 4.3
gy = 3.53
gz = 1.98
00Nam
ESR / 233
UV-VIS spectroscopy, electrochemistry
[C57H57NO2OsP4] •+
chemical reaction
84Smi
2.006
189
tBu
Ph2P
N
ESR / 293
Os: 0.469(4)
H: 0.162(6)
14
N: 1.384(12)
chemical reaction
2.006
dichloromethane
•+
O
PPh2
Os
PPh2
Ph2P
CO
[C57H57NO2P4Ru] •+
84Smi
99
tBu
Ph2P
N
Ru
Ph2P
dichloromethane
•+
O
ESR / 293
PPh2
Ru: 0.287(4)
Ru: 0.417(6)
H: 0.163(5)
14
N: 1.379(4)
101
PPh2
CO
[C58H52FeN6O3X] •
chemical reduction
CH3
X
H3C
N
N
Fe
N
N
O
O
H3C
N
O
NH
•
toluene, X = Br, Cl, F
ESR / 8–120
86Fie
Fe:
gx = 6.0
gy = 6.0
gz = 2.0
splitting of Fe signal
due to interaction
with nitroxyl
unpaired electron:
17.0 mT
NO:
gx = 2.0089
gy = 2.0062
gz = 2.0027
splitting of the NO
signal: 50.0 mT
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
191
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C54H49NO3P4Ru] •2+
chemical reaction
2.006
84Smi
dichloromethane
ESR / 293
H: 1.175(3)
14
N: 1.054(3)
31
P: 1.75
electrochemically generated
1.9980
90Kai4
1.9980
99Kle
• 2+
CO
Ph2P
PPh2
O
N
PPh2 tBu
Ru
Ph2P
CO
[C60H50N12Ru2] •3+
(bpy)2Ru
N
Me
Ph
Ph
N
• 3+
acetonitrile
ESR / 300
Me
N
N
Ru(bpy)2
HMO calculations
[C60H50N12Ru2] •3+
N
Ru(bpy)2
acetone
• 3+
Ru(bpy)2
N
N Ph
H3C
Ph N
reduction with Bu4NBH4
ESR / 298
ESR / 110
CH3
gx = 1.97932
gy = 1.99632
gz = 2.019
electrochemistry, UV-VIS spectroscopy,
spectroelectrochemistry
[C60H60FeN4O] • +
chemical oxidation
H3C
NO
Fe N
N
N
CH3
H3C
H3C
CH3
H3C
Landolt-Börnstein
New Series II/26A2
•+
CH3
CH3
CH3 H3C
CH3
CH3
H3C
H3C H C
3
dichloromethane / methanol
5:1
96Fuj
geffx = 4.47
geffy = 3.50
geffz = 1.98
90Bil
ESR / 4
chemical oxidation
toluene / methanol 4:1
CH3
g1 = 3.6
g2 = 1.98
ESR / 4.2
Mössbauer spectroscopy
192
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C61H36N4ORu] • +
chemical oxidation with Br2 or I2
2.000
97Che
•+
Ph
ESR / 77
CO
N
Ru
N
N
N
Ph
Ph
electrochemistry, UV-VIS, IR and NMR spectroscopy
Ph
[C64H52CuN8P2Ru] •2+
Cu(PPh3)2
N
N
N
N
Ru(bpy)2
• 2+
1.9952
1,2-dichloroethane
14
91Mat1
N: 0.24
electrochemistry, UV-VIS spectroscopy
chemical oxidation with Br2 or I2
•+
Ph
CO
N
Ru
N py N
97Che
dichloromethane
Ph
electrochemistry, UV-VIS, IR and NMR spectroscopy
[C70H44N6Ru] • +
•+
Ph
py
N
Ru
N py N
1.999
ESR / 77
N
Ph
Ph
electrochemically generated
ESR / RT
[C66H40N5ORu] • +
Ph
dichloromethane
chemical oxidation with Br2 or I2
2.000
dichloromethane
ESR silent at room
temperature
ESR / 77
N
97Che
Ph
Ph
electrochemistry, UV-VIS, IR and NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
193
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C70H54N8O2P2Ru2] •3+
electrochemically
generated
g1 = 2.051
g2 = 2.026
g3 = 1.981
89Ern
• 3+
Ru(bpy)2
acetone
O
PPh2
ESR / 4
acetonitrile
Ph2P
O
2.0112
ESR / 298
(bpy)2Ru
[C76H44FeMnN13] •+
chemical oxidation
[(TPP)Mn-N-Fe(Pc)] •+
THF
2.003
01Don
ESR / 78
IR, Mössbauer and Raman spectroscopy
[C80H104Fe2N12O17] 2•
NO3
N
Fe
N
N
O
O
O
Fe
O
O
2•
NO3
N
reaction of iron dimer with 2.00
95Gol
phenoxyl radical
no hyperfine structure
dichloromethane / THF
3:1
ESR / 10
XDK
H3C COOH HOOC CH3
O
O
O
CH3
= H3C
N
N
O
O
XDK
CH3
H3C
O
O
O
H3C
H3C N
tBu
N
=
O
N
N
tBu N N CH3
magnetic susceptibility
[C86H65Cl4N4O4Os4P8] • −
•
[Osf]
[Osf]
N
N
C
C
C
C
N
[Osf]
2.0005
1,2-dichloroethane
ESR / 298
N
[Osf]
[Osf] = Os(P(iPr)3)2(CO)(H)Cl
Landolt-Börnstein
New Series II/26A2
electrochemically
generated
electrochemistry, magnetic data, UV-VIS and IR
spectroelectrochemistry
97Bau
194
3.9 Complexes of group 8 (Fe, Ru, Os)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C86H65Cl4N4O4Os4P8] • −
electrochemically
generated
2.0124
97Bau
[Osf]
[Osf]
N
C
N
C
C
N
C
N
[Osf]
•
1,2-dichloroethane
ESR / 298
ESR / 110
[Osf]
g|| = 2.0065
g⊥ = 2.0160
[Osf] = Os(P(iPr)3)2(CO)(H)Cl
electrochemistry, magnetic data, UV-VIS and IR
spectroelectrochemistry
[C88H58Fe2N10O6] •+
chemical oxidation
•+
2.0016
91Ass
dichloromethane
ESR / 118
O2N
NO N
Fe
N
N
O
O2N
N
N
Fe
N
N
UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2