Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
195
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
g1 = 2.024
g2 = 1.986
88Yok
3.10 Complexes of group 9 (Co, Rh, Ir)
[C6RhS10] • 1.5−
chemical reaction
• 1.5−
S
C S
C S
C S
S
Rh
powder
ESR / 77
2
dimerisation via Rh-Rh bond postulated
UV-VIS and X-ray photoelectron spectroscopy
[C15H18CoN3O12] •+
chemical reaction
2.0038
acetic acid
14
•+
Me
Co
O
NO2
O
ESR / ENDOR / 283
N: 2.760
H(3 H): 0.039
H(3 H): 0.013
chemical reaction
2.0036
acetic acid /
dichloromethane
H(1 H): 1.88
3
92Div
Me
[C15H21CoO6] •+
•+
Me
O
Co
O
ESR / var. T
3
Me
deuteration experiments
[C18H20Cl4CoN2O4] •
Cl
•
Cl
O
Cl
O
O
acacen =
H3 C
CH3
−
[C18H20CoN4O2] •2−
• 2−
tBu
O
Me
59
86Har
Co: 1.18
59
Co: 1.27
N
electrochemistry
chemical reaction
2.002
dichloromethane
59
ESR / 298
Co(CN)4
99Arz
Co: 0.88
H: 0.26
crystal structure, UV-VIS and IR spectroscopy
[C18H23ClIrN4O2] •
electrolytic reduction
•
Me
N O
IrCp*Cl
N
toluene
ESR / RT
2
O
2.0053
dimethylformamide
Cl
O
chemical reaction
ESR / RT
Co(acacen)
tBu
95Bru2
1.9926
96Hei2
dichloromethane
ESR / 295
N
N
Landolt-Börnstein
New Series II/26A2
electrochemistry, IR and UV-VIS spectroelectrochemistry
196
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C19H36CoO2S4] •
chemical reaction
2.0013
86Har
toluene
59
•
tBu
O
ESR / RT
Co(sacsac)2
O
tBu
CH3
S
sacsac =
Co: 0.99
H: 0.325
dimethylformamide
2.0016
ESR / RT
59
Co: 0.99
H: 0.320
−
S
CH3
electrochemistry
[C21H19CoN5O4] •
•
O
O
N
N
chemical reaction
2.02
methanol
59
96Cha
Co: 1.180
ESR / 100
N
Co
N O N
2
[C22H20CoN4O2S4] •2−
tBu
• 2−
O
Co(mnt)2
chemical reaction
2.0035
dimethylformamide
59
ESR / RT
O
86Har
Co: 1.15
H: 0.30
tBu
−
mnt =
−
S
CN
S
CN
electrochemistry
[C22H20CoF12O2S4] •2−
• 2−
tBu
O
Co(pfmdt)2
chemical reaction
2.0055
dimethylformamide
59
ESR / RT
86Har
Co: 1.19
H: 0.29
O
tBu
−
pfmdt =
S
CF3
S
CF3
−
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
197
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C22H25ClIrN4O2] •
electrolytic reduction
1.9884
96Hei2
dichloromethane
193
O
Me
•
Me
N O
ESR / 295
IrCp*Cl
N
Ir: 0.69
Ir: 0.65
14
N(5): 0.64
14
N(10): 0.33
H(2 H: 6,9): 0.33
191
N
N
electrochemistry, IR and UV-VIS spectroelectrochemistry
[C24H12CoF9O6S3] •+
Co
•+
CF3
O
O
chemical reaction
2.0030
acetic acid /
dichloromethane
H(2 H): 0.430
H(2 H): 0.310
92Div
ESR / 263
3
S
[C26H24N6Rh2] •+
•+
(nbd)
Rh
N
N N
N
F3C
Landolt-Börnstein
New Series II/26A2
H(1 H): 0.59
H(1 H): 0.18
H(2 H): 0.14
chemical reduction
2.0062
dichloromethane
Aiso(Rh) = –28.6
ESR / 300
103
chemical reaction
2•
CF3 CF3
O Rh
O
O
ESR / 353
89Koh
Rh: < 0.07
N: 0.33
14
N: 0.66
(coordinated)
nbd =
[C26H36F12N2O10Rh2] 2•
O
2.0075
14
N N
Rh
(nbd)
N
acetic acid
O
Rh O
O
CF3
powder
ESR / RT
O
O
2.00
N
O
crystal structure, magnetic susceptibility, UV-VIS
spectroscopy
86Fel
198
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C26H36F12N2O12Rh2] 2•
chemical reaction
2.0054
86Fel
OH
2•
CF3 CF3
O
N
O Rh
O
O
O
Rh O
O
F3C
ESR / RT
O
O
N
O
CF3
OH
[C26H40CoN2O4] •
tBu
•
O
Co(acacen)
tBu
O
H3 C
CH3
−
chemical reaction
2.0017
toluene
59
86Har
Co: 1.10
H: 0.32
THF
2.0019
ESR / RT
59
N
2
Co: 1.11
H: 0.32
electrochemistry
[C27H34N3O6Rh2] •
[Rh2(O2CCH3)3(L)]
magnetic susceptibility, UV-VIS spectroscopy
ESR / RT
O
acacen =
powder
electrochemical reduction
•
1.99
86Bea
spin trapping
2.008
84Ham
toluene
14
acetonitrile
ESR / < 123
L =
N
N
N
electrochemistry
[C27H36CoN4O5] •
•
ESR / RT
N
N: 1.28
H(β): 0.768
O
O
N
Co
N
O
O
N
O
Me
Me
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
199
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C30H27N2O6Rh2] •
electrochemical reduction
1.99
86Bea
chemical reaction
2.0010
86Har
toluene
59
[Rh2(O2CCH3)3(L)]
•
acetonitrile
ESR / < 123
L =
N
N
N
electrochemistry
[C30H36CoN2O4] •
•
tBu
O
Co(salen)
O
tBu
ESR / RT
THF
2.0013
ESR / RT
59
N
salen =
O−
2
[C31H20CoO6P2] •
O
O
O
Ph2
P
Co(CO)3
P
Ph2
•
Co: 1.05
H: 0.33
Co: 1.06
H: 0.33
electrochemistry
irradiation of precursor in the
presence of ligand
2.004
95Mey
31
P: 0.97 (2P)
dichloromethane
ESR / 298
IR spectroscopy, electrochemistry
dichloromethane
2.0041
ESR / 298
59
89Mao1
Co: 0.105
P: 0.972
31
THF
2.0042
ESR / 300
59
98Duf
Co: 0.1299
P: 1.1047
31
temperature dependence of hyperfine splitting
[C31H20CoO6P2] •
O
O
O
Ph2
P
Co(CO)3
P
Ph2
(continued)
Landolt-Börnstein
New Series II/26A2
•
chemical reaction
2.0042
toluene
31
P: 1.106
Co: 0.151
59
ESR / 190–300
91Mao
200
3.10 Complexes of group 9 (Co, Rh, Ir)
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
[C31H20CoO6P2] • (continued)
dichloromethane
2.0042
ESR / 190–300
31
[Ref. p. 329
Ref. /
add. Ref.
P: 1.099
Co: 0.120
59
THF
2.0042
ESR / 190–300
31
P: 1.105
Co: 0.130
59
[C32H23CoNO5P2] •
O
H3C N
O
Ph2
P
Co(CO)3
P
Ph2
irradiation of precursor in the
presence of ligand
•
N
31
P: 1.125 (2P)
dichloromethane
ESR / 298
IR spectroscopy, electrochemistry
[C32H38Cl2Ir2N6] •+
IrCp*Cl
N N
N
95Mey
electrochemically generated
•+
1.9917
99Kai
acetonitrile
ESR / 293
N N
IrCp*Cl
acetonitrile
g1 = 2.019
ESR / 110
g2 = 1.991
g3 = 1.962
UV-VIS and IR spectroelectrochemistry
[C32H38Cl2N6Rh2] •+
electrochemically generated
1.9990
99Kai
103
RhCp*Cl
N N
N
N
N N
RhCp*Cl
•+
acetonitrile
ESR / 293
acetonitrile
ESR / 110
Rh: 0.53
N: 0.24 (2N)
14
N: 0.74 (2N)
14
g1 = 2.002
g2 = 2.002
g3 = 1.9914
UV-VIS and IR spectroelectrochemistry
acetonitrile
g⊥ = 2.0019
ESR / 3.4
g|| = 1.9914
97Kai
UV-VIS spectroscopy, electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
201
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C32H53CoN3O3] •2+
electrochemically generated
2.0047
97Sok2
acetonitrile / dichloromethane
59
• 2
iPr
N
iPr N
ESR / 298
O Me
Co: 0.6
H(benzylic): 0.655
Co
N
O
Me
O
tBu
crystal structure, UV-VIS and NMR spectroscopy,
electrochemistry, resonance Raman
tBu
[C33H30CoN3O12S3] •+
•+
NO2 Me
O
Co
S
O
[C33H30CoN3O12S3] •+
•+
Me
O
O 2N
Co
S
O
[C33H48Cl4CoN3O3] 2•2+
2• 2+
iPr
N
O
Cl
O
Co: 0.52
chemical reaction
2.0094
trifluoroacetic acid /
dichloromethane
59
95Bru2
Co: 0.58
electrochemically generated
g = 2 (broad)
acetonitrile
g = 4.12 (∆m = 2)
ESR / 2.8–150
D = 0.3 cm–1
97Sok2
Cl
Cl
O
59
Cl
Co
N
trifluoroacetic acid /
dichloromethane
95Bru2
ESR / var. T
3
Me
iPr N
2.0078
ESR / var. T
3
Me
chemical reaction
tBu
crystal structure, UV-VIS, NMR and resonance Raman
spectroscopy, electrochemistry
tBu
[C34H50Cl2CoN2O6] 2•
2•
chemical oxidation
2.0057
toluene, DMSO, pyridine
H(2 H): 0.161
H(2 H): 0.810
tBu
ESR / 293 and 77
O
tBu
O
CoCl2
NHO
2
Landolt-Börnstein
New Series II/26A2
95Zav
202
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C34H36F28N2O10Rh2] 2•
chemical reaction
2.00
86Fel
2•
C3F7 C3F7
O
N
O Rh
O
O
ESR / RT
O
O
O
Rh O
N
O
O
C3F7 C3F7
crystal structure, magnetic susceptibility, UV-VIS spectroscopy
[C34H60CoN4O2] •2+
• 2+
N
Co
dichloromethane
59
tBu
tBu
• 2+
CH3
2.004
dichloromethane
59
Co
O
Ph
O
00Mül
Co: 0.513
H(CH2): 0.463,
aH/aD = 6.5
H(CH3): 0.246
H(benzylic): 0.125
H(benzylic): 0.043
crystal structure, electrochemistry, UV-VIS spectroscopy,
resonance Raman
MeO
[C36H46CoN5O] • +
•+
Et
Et
Et
N NO
N
Co
N
N
Et
Co: 1.215
N: 0.856
H(anilino): 1.017
H(benzyl): 0.920
H(benzyl): 0.38
electrochemically generated
ESR / 298
O Ph
N
00Pen
crystal structure, electrochemistry, spectroelectrochemistry
[C35H45CoN3O4] •2+
H3C N
2.0023
ESR / 10
N
O
N
O
H
tBu
N
electrochemical generation
14
N
tBu
powder
Et
electrochemically generated
2.0026
dichloromethane
59
ESR / 293
85Fuj
Co: 0.33
H(2 H): 0.40
Et
Et
Et
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
203
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C37H25ClO5P2W] •−
electrochemical reduction
2.0044
98Duf
1,2-dichloroetane /
dichloromethane
31
O
Ph2
P
W(Cl)(CO)2(CPh)
P
Ph2
O
O
•−
ESR / 300
temperature dependence of hyperfine splitting and linewidths
[C37H48CoN5O] • +
•+
Et
Et
Et
Et
Et
Me
electrochemically generated
2.0026
dichloromethane
59
ESR / 293
N NO
N
Co
N
N
P: 0.8644
85Fuj
Co: 0.33
H(2 H): 0.71
Et
Et
Et
electrochemistry, UV-VIS spectroscopy
[C38H46CoN4] •+
chemical reaction
[Co(OEP)(C2H2)] •+
dichloromethane
2.002
97Set
ESR / 77
ESR / 4.2
CoII signal
equilibrium with dimer
[C38H54CoN5O] • +
Me
•+
Et Et
Et
N NO
N
Co
N
N
Et
Et
Et
Me
Et
Et
•+
Me
N NO
N
Co
N
N
Et
59
Co: 0.28
H(2 H): 0.67
electrochemically generated
2.0057
dichloromethane
59
ESR / 293
Co: 0.28
H(2 H): 0.45
Et
Et
Landolt-Börnstein
New Series II/26A2
Et
Et
dichloromethane
85Fuj
electrochemistry, UV-VIS spectroscopy
[C38H54CoN5O] • +
Me
2.0057
ESR / 293
Et
Et
Et
electrochemically generated
electrochemistry, UV-VIS spectroscopy
85Fuj
204
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C38H54CoN5O] • +
electrochemically generated
2.0057
85Fuj
dichloromethane
59
Et Me
Et
Et
Et
NO
N
Me
N
Co
N
Et
N
Et
Et
Et
•+
ESR / 293
electrochemistry, UV-VIS spectroscopy
[C40H26Co2O7P2] •−
O
O
O
Ph2
P CO Co(CO)
3
Co
P
Ph
Ph2 H
•−
IrCp*Cl
N
H3 C
N
electrochemical reduction
2.0039
THF
59
98Duf
Co: 0.0059
P: 0.820
31
ESR / 300
measurement in solvent mixtures, temperature dependence of
hyperfine splitting and linewidths
[C40H48Cl2Ir2N4] •+
N
Co: 0.27
H(1 H): 0.67
H(1 H): 0.45
electrochemically generated
•+
CH3
1.968
99Kai
acetonitrile
calculated
N
IrCp*Cl
acetonitrile
ESR / 110
g1 = 1.994
g2 = 1.994
g3 = 1.9156
UV-VIS and IR spectroelectrochemistry
electrochemical reduction
1.975
acetonitrile
g1 = 2.009
g2 = 2.000
g3 = 1.916
ESR / 3.5
00Ber
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C40H48Cl2N4Rh2] •+
electrochemical reduction
RhCp*Cl
N
N
H3C
N
•+
CH3
1.9934
97Kai
acetonitrile
ESR / 270
N
RhCp*Cl
(continued)
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
205
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C40H48Cl2N4Rh2] •+ (continued)
electrochemically generated
1.9934
99Kai
acetonitrile
ESR / 270
UV-VIS and IR spectroelectrochemistry
electrochemical reduction
1.995
acetonitrile
g1 = 1.9975
g2 = 1.9975
g3 = 1.990
ESR / 3.5
00Ber
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C42H50CoN2O4] 2•
tBu
O•
tBu
O
2•
chemical oxidation
g = 2.0023
THF
59
86Iva
Co: 1.17
ESR / 293
N
Co
N
•
O
O
tBu
tBu
[C42H59N4O2PRh] •
chemical reaction
[Rh(OEP)(PEt3)(O2)] •
toluene
g1 = 2.002
g2 = 1.982
g3 = 1.964
00Col
ESR / 77
NMR and UV-VIS spectroscopy, determination of stability
constants
[C42H59N4PRh] •
chemical reaction
[Rh(OEP)(PEt3)] •
toluene
ESR / 77
g1 = 2.018
g2 = 2.018
g3 = 1.982
00Col
31
P: 0.793
NMR and UV-VIS spectroscopy, determination of stability
constants
Landolt-Börnstein
New Series II/26A2
206
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C42H60CoO6]3 •
chemical reaction
1.998
94Lan
toluene
59
3•
tBu
O
Co: 2.26
ESR / 77
Co
O
tBu
3
crystal structure, magnetic measurements, NMR spectroscopy
[C42H60CoN3O6] •+
•
electrochemically generated
2.004
acetonitrile/dichloromethane
59
97Sok2
Co: unresolved
N
O
O
ESR / 77
Co
N
N
O
OMe
N
O
=
MeO
O
N
UV-VIS and NMR spectroscopy, electrochemistry
[C44H28CoN5O] •+
•+
Ph
Ph
N NO
N
Co
N
N
electrochemical oxidation
2.0049
dichloromethane
59
88Kad1
Co: 0.701
ESR / RT and 123
Ph
electrochemistry, UV-VIS and IR spectroscopy
Ph
[C44H56ClIr2N4] •+
IrCp*Cl
N
N
•+
electrochemical reduction
1.995
acetonitrile
g1 = 2.0411
g2 = 2.0068
g3 = 1.9362
ESR / 3.5
00Ber
N
N
Cp*Ir
electrochemistry, UV-VIS and IR spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
207
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H56ClN4Rh2] •+
electrochemical reduction
2.004
00Ber
acetonitrile
g1 = 2.015
g2 = 2.001
g3 = 1.996
•+
RhCp*Cl
N
N
ESR / 3.5
N
N
Cp*Rh
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C45H33CoO6] •+
•+
Ph
O
chemical reaction
2.0052
acetic acid /
dichloromethane
H(2 H, o): 0.144
H(2 H, m): 0.045
H(1 H, p): 0.188
Co
O
ESR / 243
3
92Div
Ph
ESR / 263
2.0034
H(4 H, o): 0.153
H(4 H, m): 0.076
H(2 H, p): 0.229
H(1 H, 3): 0.229
[C45H51CoN6O2] •+
chemical oxidation
•+
Et
Et
Et
N py
N
Co
O
N
py N O
Et
Et
Et
Et
crystal structure, electrochemistry
[C46H30Co2O7P2] •−
O
O
Ph2
P
Co (CO)2
Co
P
(CO)2
Ph2
•−
Ph
O
O
2.0035
THF / dichloromethane
59
98Duf
Co: 0.0141
P: 0.924
ESR / 300
Ph
Ph2
P CO Co(CO)
3
Co
P
Ph
Ph2 Ph
Landolt-Börnstein
New Series II/26A2
electrochemical reduction
31
temperature dependence of hyperfine splitting and linewidths
[C46H30Co2O7P2] •−
O
97Att
ESR / 77
Et
O
dichloromethane /
methanol
gx,y = 1.996
gz = 2.018
•−
electrochemical reduction
2.0036
THF
59
98Duf
Co: 0.0057
P: 0.8066
31
ESR / 300
measurement in solvent mixtures, temperature dependence of
hyperfine splitting and linewidths
208
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C46H32CoN4O] •+
electrochemical reduction
2.01
86Kad
[Co(TPP)(CH3CHO] •+
benzonitrile
ESR / 123
electrochemistry, UV-VIS spectroscopy
[C46H35ClN5Rh] •+
electrochemical oxidation
[Rh(TPP)Cl(HN(CH3)2)] •+
benzonitrile
2.000
85Kad3
ESR / < 123
electrochemistry, UV-VIS spectroscopy
[C46H36F20N2O10Rh2] 2•
chemical reaction
2•
C6F5
O
N
O
O
O
ESR / RT
N
magnetic susceptibility, UV-VIS spectroscopy
[C48H35CoO5P2] •
O
powder
O
C6F5
O
86Fel
O
Rh O
O
O Rh
O
O
C6F5
C6F5
2.00
Ph2
P
Co(PPh3)(CO)2
P
Ph2
•
dichloromethane
2.0034
ESR / RT
59
89Mao1
Co: 0.015
P: 0.822
31
chemical reaction
2.0038
toluene
31
91Mao
P: 0.969
59
Co: 0.025
ESR / 190–300
dichloromethane
2.0038
ESR / 190–300
31
P: 0.940
59
Co: < 0.018
THF
2.0038
ESR / 190–300
31
P: 0.968
59
Co: < 0.026
(continued)
evidence of two isomers in equilibrium
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
209
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H35CoO5P2] • (continued)
irradiation of precursor in
the presence of ligand
2.003
95Mey
dichloromethane
31
P(1): 0.82
P(2): 0.82
31
ESR / 298
IR spectroscopy, electrochemistry
THF
2.0038
ESR / 300
31
98Duf
P: 0.969
temperature dependence of hyperfine splitting
[C49H37ClCoN4O3] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
O
X=
O O
2.0058
88Koh
2.0062
88Koh
chemical oxidation
2.0054
95Zav
toluene, DMSO, pyridine
H(2 H): 0.160
H(2 H): 0.775
ESR / 278
tBu
UV-VIS spectroscopy
[C51H33ClCoN4O3] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
O
O O
ESR / 278
X=
UV-VIS spectroscopy
[C51H81Cl2CoN6O6] 3•
3•
tBu
ESR / 293 and 77
O
O
tBu
HN
CoCl2
NH2
3
Landolt-Börnstein
New Series II/26A2
210
3.10 Complexes of group 9 (Co, Rh, Ir)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C51H78CoN3O3] •+
electrochemically generated
2.004
97Sok2
acetonitrile / dichloromethane
59
•
Co: unresolved
N
O
O
ESR / 77
Co
N
N
O
tBu
N
O
=
tBu
O
N
UV-VIS and NMR spectroscopy, electrochemistry
[C56H60N4P2Rh] •
chemical reaction
[Rh(TPP)(PEt3)2] •
toluene
g1 = 2.021
g2 = 2.021
g3 = 1.973
00Col
ESR/ 77
NMR and UV-VIS spectroscopy, determination of stability constants
[C56H80CoN2O4] •
•
tBu
Co
N
O
tBu
tBu
1.9974
pentane, toluene
59
ESR / var. T
tBu
O
chemical reaction
2
Co: 0.93
H: 0.34
chemical reaction
2.005
dichloromethane
59
ESR / RT
88Lar
90Mai
Co: 0.93
H: 0.34
electrochemical reduction to
(2•–) state
2.003
electrochemical oxidation to
(2•+) state
2.005
59
Co: 1.59
N: 0.76
H(2 H): 0.41
H(2 H): 0.26
14
crystal structure, electrochemistry, magnetic moment, UV-VIS and
IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
211
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C58H38CoN4O6] •+
photochemically generated
2.0082
88Koh
[Co(TPP)(X)2] •+
benzene
2.0047
88Koh
2.0063
88Koh
2.0054
88Koh
2.0047
88Koh
C (O )O 2
ESR / 278
X =
UV-VIS spectroscopy
[C62H57ClCoN4O6] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
ESR / 278
X =
C (O )O
2
UV-VIS spectroscopy
[C62H59ClCoN4O6] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
ESR / 278
X =
C (O )O
2
UV-VIS spectroscopy
[C62H61ClCoN4O6] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
ESR / 278
X=
C(O)O2
UV-VIS spectroscopy
[C64H59ClCoN4O6] •+
photochemically generated
[Co(TPP)(Cl)(X)] •+
benzene
X =
C (O )O 2
ESR / 278
UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
212
3.10 Complexes of group 9 (Co, Rh, Ir)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C88H84Cl12CoN8O4]
•x
x = 2−:
• 2−
R
chemical reduction
Ref. /
add. Ref.
92Mil
2.0038
dimethylformamide, THF,
diethylether or acetonitrile
N
R
N
N
N
Co
N
N
N
R
N
R
ESR / RT
x = 2+:
chemical oxidation
Cl
2.0012
benzene or bromobenzene
Cl
R
g-Factor /
a-Value [mT]
[Ref. p. 329
tBu
=
Cl
O−
tBu
ESR / RT
(–H) x = 0:
chemical oxidation
2.0045
dimethylformamide
ESR / RT
UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2