118
3.8 Complexes of group 7 (Mn, Tc, Re)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.013
93Mat2
3.8 Complexes of group 7 (Mn, Tc, Re)
[C9ReS15] •
S
electrochemical oxidation
•
S
Re
powder
S
S
S
ESR / 77
3
electrochemistry, UV-VIS, IR and X-ray photoelectron spectroscopy,
electrical conductivity
[C10H8MnO6] •
photochemical reaction
•
O
THF
Mn(CO)4
ESR / 293
O
THF
[C11H6ClN4O3Re] •−
•−
N
N
92Reb
55
Mn: 0.515
H(3): 1.088
H(6): 1.088
ESR / 213
H(3): 0.730
H(3): 1.460
H(6): 0.730
H(6): 1.460
electrochemically generated
2.0026
98Ber1
acetonitrile
185,187
96Kle
Re: 1.00
ESR / 250
Re(CO)3Cl
N
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C11H6ClN4O3Re] •−
•−
N
N
electrochemically generated
2.0023
THF
185,187
96Kle
Re: 1.6
ESR / RT
Re(CO)3Cl
N
N
electrochemistry, IR spectroscopy
[C11H6ClN4O3Re] •−
•−
N
N
electrochemically generated
2.0028
THF
185,187
96Kle
Re: 0.8
ESR / RT
Re(CO)3Cl
N
N
electrochemistry, IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
119
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C11H6ClN4O3Re] •−
electrochemically generated
2.0018
98Ber1
acetonitrile
185,187
96Kle
•−
N
N
Re: 1.4
ESR / 250
Re(CO)3Cl
N
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C11H16N2O3Re] •
•
iPr
N
H
irradiation of corresponding
dimers
N
iPr
88And
185,187
ESR / 293
Re: 3.867
N: 0.702
H(imine): 0.464
H(CH): 0.163
toluene
2.0059
ESR / 203
185,187
cyclohexane
Re(CO)3
H
2.0051
14
Re: 3.841
N: 0.636
H(imine): 0.4489
14
[C11H18N2O3ReS] •
•
tBu
N
THF
185,187
96Kle
Re: 2.19
N: 0.68 / 0.50
ESR / RT
N
tBu
electrochemistry, IR spectroscopy
[C12H12N2O3Re] •
irradiation of corresponding
dimers
•
iPr
N
H
2.0009
14
Re(CO)3
S
electrochemically generated
toluene
Re(CO)3
ESR / 243
N
[C13H6ClN4O3Re] •−
•−
N
N
2.0051
Re: 2.814
N: 0.554
H(imine): 0.465
14
electrochemically generated
2.0003
98Ber1
acetonitrile
185,187
96Kle
Re: 1.6
ESR / 250
Re(CO)3Cl
N
N
Landolt-Börnstein
New Series II/26A2
88And
185,187
electrochemistry, UV-VIS and IR spectroelectrochemistry
120
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C13H8BrN2O3Re] •−
electrochemically generated
2.0023
87Kai1
185,187
acetone
•
N
Re: 1.2
Br: 1.0
79,81
90Kai1
2.0032
87Kai1
ESR / 300
Re(CO)3Br
N
[C13H8ClN2O3Re] •−
electrochemically generated
185,187
acetone
•
N
Re: 1.2
Cl: 0.2
90Kai1
35,37
ESR / 300
98Ber1
Re(CO)3Cl
96Kle
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C13H8ClN4O3Re] •−
•
N
N
Re(CO)3Cl
chemical oxidation
2.0041
dichloromethane or
1,2-dichloroethane
185,187
00Har
Re: 2.38
ESR / 298
N
N
crystal structure, IR and UV-VIS spectroscopy, electrochemistry,
spectroelectrochemistry
[C13H9N2O3Re] •−
•
N
electrochemically generated
2.0029
acetonitrile
185,187
97Sch
Re: 1.79
ESR / 298
Re(CO)3H
N
electrochemistry
[C13H9N5O3Re] •
electrochemically generated
•
N
N
acetonitrile
98Ber1
185,187
Re: 1.82
96Kle
ESR / 250
Re(CO)3(NCCH3)
N
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
121
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C13H20ClN2O3Re] •−
electrochemically generated
2.0032
96Kle
THF
185,187
•−
tBu
N
Re: 1.9
ESR / RT
Re(CO)3Cl
N
tBu
electrochemistry, IR spectroscopy
[C13H20MnN2O3] •
irradiation of corresponding
dimers
•
tBu
N
toluene
Mn(CO)3
ESR / 203
N
tBu
[C13H20N2O3Re] •
irradiation of corresponding
dimers
•
tBu
N
cyclohexane
Re(CO)3
ESR / 343
N
tBu
2.0046
88And
55
Mn: 0.847
N: 0.734
H(imine): 0.503
14
2.0046
88And
185,187
96Kle
Re: 3.555
N: 0.734
H(imine): 0.503
14
benzene
2.0036
ESR / 293
185,187
Re: 3.561
N: 0.726
H(imine): 0.465
14
electrochemistry, IR spectroscopy
[C13H21N2O3Re] •−
•−
iPr
N
electrochemically generated
2.0051
THF
185,187
96Ros
Re: 4.87
ESR / 293
Re(Et)(CO)3
N
iPr
electrochemistry, IR spectroscopy
[C14H6Br2N4O6Re2] •−
•−
N
N
Br(CO)3Re
electrochemically generated
2.0005
acetone
185,187
Re: 1.2
Br: 0.8
79,81
ESR / RT
Re(CO)3Br
N
N
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2
90Kai1
122
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C14H6Cl2N4O6Re2] •−
electrochemically generated
2.0005
90Kai1
acetone
185,187
•−
N
Re: 1.2
Cl: 0.2
35,37
N
Cl(CO)3Re
Re(CO)3Cl
N
N
electrochemistry, UV-VIS spectroscopy
[C14H8Cl2N2O8Re2] •−
H3C
O
•
Re(CO)3Cl
N
O
chemical reaction
2.0055
89Bes1
acetonitrile
g1 = 1.9721
g2 = 2.0043
g3 = 2.0430
89Bes2
ESR / 4
N
CH3
Re(CO)3Cl
electrochemistry, UV-VIS and IR spectroscopy
[C14H8F3N2O6SRe] •−
•
N
electrochemically generated
2.0031
acetonitrile
185,187
97Sch
Re: 1.08
ESR / 298
Re(CO)3(O3SCF3)
N
electrochemistry
[C14H8MnN2O4] •
•
N
Mn(CO)4
reduction with sodium
amalgam
2.0018
THF
14
ESR / 220–260
N
94Bro
55
Mn: 0.17
N: 0.36
H(3): 0.071
H(4): 0.42
H(5): 0.123
H(6): 0.104
electrochemistry, EHMO calculations
[C14H8N2O5Re] •
•
N
electrochemically generated
2.0010
THF
185,187
96Kle
Re: 1.6
ESR / RT
Re(CO)3(CO2)
N
electrochemistry, IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
123
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C14H9N2O5Re] •−
electrochemically generated
2.0035
97Sch
acetonitrile
185,187
•
N
Re: 1.14
ESR / 298
Re(CO)3[C(O)OH]
N
electrochemistry
[C14H11MnN2O2] •−
•
'
Cp (CO)2Mn N
CN
reduction with potassium metal
2.0005
THF
55
87Gro
Mn: 0.655
N(py): 0.725
14
N(CN): 0.211
H: 0.154 (2H)
H: 0.211 (2H)
14
ESR / RT
electrochemistry, UV-VIS, IR and NMR spectroscopy
[C14H11N2O4Re] •−
•
N
electrochemically generated
2.0031
acetonitrile
185,187
97Sch
Re: 1.92
ESR / 298
Re(CO)3(OCH3)
N
electrochemistry
[C14H16MnO6] •
photochemical reaction
•
O
O Mn(CO)4
Landolt-Börnstein
New Series II/26A2
toluene
ESR / 293
92Reb
55
Mn: 0.369
H(1): 0.012
H(4): 0.254
H(5): 0.322
H(6): 0.301
H(7): 0.071
124
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C15Re2S25] •−
electrochemical oxidation
2.01
96Mat
•−
S
S
S
S
S
S
ESR / 77
S
S
S
S
S
S
S
S
S
S
S
S
Re
Re
S
S
S
crystal structure, electrochemistry, UV-VIS and IR
spectroscopy, electrical conductivity
S
S
S
S
[C15H6ClMoN4O7Re] •−
Mo(CO)4
N
N
N
powder
•
electrochemical generation
2.0014
1,2-dichloroethane
185,187
91Mat1
Re: 1.1
ESR / 298
N
Re(CO)3Cl
electrochemistry, UV-VIS spectroscopy, luminescence
[C15H8N2O3Re] •
•
N
Re(CO)3
irradiation of corresponding
dimers
2.0040
toluene
14
ESR / 203
88And
185,187
Re: 2.088
N: 0.360
H(imine): 0.299
N
[C15H11N2O4Re] •−
•
N
electrochemically generated
2.0024
acetonitrile
185,187
97Sch
Re: 1.96
ESR / 298
Re(CO)3[C(O)CH3]
N
electrochemistry
[C15H11N3O3Re] •
•
N
electrochemically generated
2.0033
THF
185,187
96Kle
Re: 2.2
ESR / RT
Re(CO)3(NCCH3)
N
electrochemistry, IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C15H23N3O3Re] •
electrochemically generated
•
tBu
N
THF
125
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
96Kle
185,187
Re: 3.72
N: 0.73
H: 0.45
14
ESR / RT
Re(NCCH3)(CO)3
N
tBu
electrochemistry, IR spectroscopy
[C16H8Br2N4O6Re2] •−
(CO)3Br
Re
N
N
N
•
electrochemically generated
2.0040
87Kai1
1,2-dichloroethane
185,187
90Kai1
Re: 2.54
Br: 0.6
79,81
ESR / 300
N
Re
(CO)3Br
[C16H8Cl2N4O6Re2] •−
(CO)3Cl
Re
N
N
N
electrochemically generated
2.0040
87Kai1
185,187
•
1,2-dichloroethane
Re: 2.54
Cl: 0.2
35,37
90Kai1
ESR / 300
electrochemistry, UV-VIS spectroscopy
N
Re
(CO)3Cl
chemical oxidation
2.0039
dichloromethane or
1,2-dichloroethane
185,187
00Har
Re (2 Re) = 2.54
ESR / 298
crystal structure, IR and UV-VIS spectroscopy,
electrochemistry, spectroelectrochemistry
[C16H21MnN3O4] •
H
•
iPr
N
Mn(CO)3(ONtBu)
[C16H21N3O4Re] •
H
•
Re(CO)3(ONtBu)
N
Landolt-Börnstein
New Series II/26A2
2.0098
toluene
14
ESR / 203
N
iPr
N
irradiation of corresponding
dimers
Mn: 0.725
N(NO): 1.455
14
N(imine): 0.096
irradiation in the presence of 2.0087
spin trap
185,187
Re: 3.046
14
N(NO): 1.360
THF
ESR / 293
88And
55
88And
126
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C16H29N2O6PRe] •
chemical reaction
2.0090
88And
benzene
185,187
•
tBu
N
H
Re(CO)3[P(OMe)3]
H
ESR / 293
Re: 3.998
P: 3.578
14
N: 0.720
H(imine): 0.448
electrochemically generated
2.0026
acetonitrile
185,187
31
N
tBu
[C17H16N2O4Re] •
•
N
97Sch
Re: 1.15
ESR / 298
Re(CO)3(THF)
N
electrochemistry
[C17H17MnN3O4] •
photolysis in presence of spin
trap
•
THF
N
94Sto2
55
Mn: 0.653
N(NO): 1.432
14
ESR / RT
Mn(ONtBu)(CO)3
N
UV-VIS and IR spectroscopy, spectroelectrochemistry
[C17H22MnO6] •
tBu
•
O
Mn(CO)3(H2O)
O
chemical oxidation
2.0045
95Har
dichloromethane
55
Mn: 0.71
H: 0.56
H: 0.28 (H2O)
96Har
irradiation in the presence of
spin trap
2.0124
88And
THF
14
ESR / 230
tBu
[C17H29N3O4Re] •
•
tBu
N
Re(CO)3(ONtBu)
185,187
Re: 3.486
N(NO): 1.401
ESR / 293
N
tBu
[C18H7BrMnO6] •
in situ photolysis
2.00465
88Wan
55
•
O
benzene
ESR / RT
Mn: 0.5625
H: 0.1642 (3H)
H: 0.0398 (4H)
Mn(CO)4
O
Br
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
127
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C18H7BrO6Re] •
in situ photolysis
2.0039
88Ho
benzene
185,187
•
ESR / RT
O
O
Re: 2.28
Re(CO)4
Br
[C18H7ClMnO6] •
in situ photolysis
2.00404
88Wan
55
benzene
•
O
ESR / RT
Mn: 0.5595
H: 0.1670 (3H)
H: 0.0403 (4H)
Mn(CO)4
O
Cl
[C18H7ClO6Re] •
•
2.0031
benzene
185,187
88Ho
Re: 2.27
ESR / RT
O
O
in situ photolysis
Re(CO)4
Cl
[C18H7MnNO8] •
in situ photolysis
2.00384
88Wan
55
benzene
•
O
ESR / RT
Mn: 0.6005
H: 0.1570 (4H)
H: 0.0359 (3H)
Mn(CO)4
O
NO2
[C18H7MnNO8] •
in situ photolysis
2.00384
55
•
O
O2 N
Landolt-Börnstein
New Series II/26A2
ESR / RT
Mn(CO)4
O
benzene
Mn: 0.5928
H: 0.1578 (4H)
H: 0.0345 (3H)
88Wan
128
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C18H7NO8Re] •
in situ photolysis
2.0030
88Ho
benzene
185,187
•
ESR / RT
O
O2N
O
Re: 2.41
Re(CO)4
[C18H7NO8Re] •
•
in situ photolysis
2.0029
benzene
185,187
88Ho
Re: 2.45
ESR / RT
O
Re(CO)4
O
NO2
[C18H8Br2N6O6Re2] •−
•−
(CO)3Br
Re
N
N N
electrochemically generated
2.0045
1,2-dichloroethane
185,187
Re: 2.2
Br: 0.5
79,81
ESR / RT
N N
90Kai1
N
Re
(CO)3Br
electrochemistry, UV-VIS spectroscopy
[C18H8Cl2N6O6Re2] •−
•−
(CO)3Cl
Re
N
N N
electrochemically generated
2.0051
1,2-dichloroethane
185,187
Re: 2.2
Cl: 0.2
35,37
ESR / RT
N N
90Kai1
N
Re
(CO)3Cl
electrochemistry, UV-VIS spectroscopy
[C18H8MnO6] •
in situ photolysis
•
O
Mn(CO)4
2.00375
88Wan
55
benzene
ESR / RT
Mn: 0.5501
H: 0.1692 (4H)
H: 0.0414 (4H)
O
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
129
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C18H8MnO6] •
photochemically generated
2.0038
86Vlc
toluene
55
•
O
tBu
tBu
Mn: 0.55
ESR / 298
O
Mn(CO)4
[C18H8O6Re] •
•
2.0033
benzene
185,187
88Ho
Re: 2.24
ESR / RT
O
O
in situ photolysis
Re(CO)4
[C18H11ClN3O3Re] •−
•−
electrochemically generated
2.0025
THF
185,187
96Kle
Re: 1.0
ESR / RT
N
N
Re(CO)3Cl
N
electrochemistry, IR spectroscopy
[C18H14Mn2N2O4] •−
•−
(CO)2CpMn
N
N MnCp(CO)2
reduction with potassium
metal
THF
ESR / 298
1.9999
86Gro
55
Mn: 0.733
H: 0.255
14
N: 0.881
NMR, IR and UV-VIS spectroscopy, electrochemistry
[C18H15N4O3Re] •+
•+
N
Re(CO)3 (N
N CH3)
electrochemically generated
2.0044
acetonitrile
185,187
ESR / 250
additional coupling at
0.8
98Ber1
Re: 1.98
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
130
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C18H20MnO6] •
chemical oxidation
2.0033
95Har
dichloromethane
55
Mn: 0.71
H: 0.335
96Har
tBu
•
O
Mn( CO)4
O
ESR / RT
[C18H20O6Re] •
photolysis
2.0022
96Har
dichloromethane
185,187
92Har
tBu
tBu
•
O
Re(CO)4
ESR / RT
O
tBu
[C18H25N3O3Re] •
H
2.0022
ESR / 295
185,187
91Van
Re: 2.82
H: 0.346
THF
2.0022
ESR / 295
185,187
chemical reaction
Re: 2.80
H: 0.36
2.0030
88And
185,187
ESR / 293
Re: 3.112
N(py): 0.491
14
N(imine): 0.652
cyclohexane
2.0028
ESR / 343
185,187
14
Re(CO)3Py
H
toluene
•
tBu
N
Re: 2.82
H: 0.346
N
tBu
Re: 3.180
N(py): 0.531
14
N(imine): 0.632
14
[C18H26MnN2O8P2] •
•
THF
N
Mn(CO)2[P(OCH3)3]2
N
reduction with sodium
amalgam
ESR / 220–260
2.0018
94Bro
55
Mn: 0.606
P: 3.489
14
N: 0.396
H(3): 0.08
H(4): 0.417
H(5): 0.14
H(6): 0.13
31
electrochemistry, EHMO calculations
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
131
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C19H7MnNO6] •
in situ photolysis
2.00387
88Wan
55
benzene
•
O
ESR / RT
Mn(CO)4
Mn: 0.5960
H: 0.1602 (3H)
H: 0.0564 (2H)
H: 0.0319 (2H)
O
NC
[C19H7NO6Re] •
•
in situ photolysis
2.0030
benzene
185,187
88Ho
Re: 2.45
ESR / RT
O
Re(CO)4
O
NC
[C19H10MnO7] •
in situ photolysis
2.00392
88Wan
55
•
O
ESR / RT
Mn: 0.5119
H: 0.1750 (3H)
H: 0.0515 (2H)
H: 0.0112 (2H)
H: 0.0255 (3 H)
in situ photolysis
2.0032
benzene
185,187
benzene
Mn(CO)4
O
H3CO
[C19H10O7Re] •
•
88Ho
Re: 2.07
ESR / RT
O
Re(CO)4
O
MeO
[C19H16N2O3Re] •
•
CH3
irradiation of corresponding
dimers
2.0043
cyclohexane
14
ESR / 343
H
N
H
N
Re(CO)3
CH3
Landolt-Börnstein
New Series II/26A2
185,187
Re: 3.660
N: 0.530
H(imine): 0.408
88And
132
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C19H17MnN3O4] •
irradiation of corresponding
dimers
2.0102
88And
•
toluene
N
Mn(CO)3(ONtBu)
ESR / 203
55
Mn: 0.694
N(NO): 1.398
14
N(imine): 0.089
14
N
[C19H17N3O4Re] •
•
N
Re(CO)3(ONtBu)
irradiation in the presence of 2.0104
spin trap
185,187
Re: 2.740
14
N(NO): 1.359
THF
88And
ESR / 293
N
[C19H20MnO7] •
•
O
tBu
tBu
•
tBu
O
toluene
55
91Van
Mn: 0.23
IR spectroscopy
[C19H20O7Re] •
O
2.0045
ESR / 180
O
Mn(CO)5
tBu
photochemically generated
photochemically generated
2.005
toluene
185,187
91Van
Re: 0.55
ESR / 193
Re(CO)5
[C19H20O7Re] •
IR spectroscopy
photochemically generated
•
2.0051
91Van
toluene
O
tBu
tBu
O
Re(CO)5
ESR / 295
THF
2.0052
ESR / 295
185,187
toluene
2.006
ESR / 193
185,187
Re: 0.15
Re: 0.19
N: 0.48
14
IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
133
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C19H21MnN3O4] •
irradiation of corresponding
dimers
2.0105
88And
•
CH3
toluene
ESR / 203
N
55
Mn: 0.688
N(NO): 1.394
14
N(imine): 0.098
14
Mn(CO)3(ONtBu)
N
CH3
[C19H21N3O4Re] •
irradiation in the presence of 2.0112
spin trap
185,187
Re: 2.720
14
N(NO): 1.353
THF
•
N
Re(CO)3(ONtBu)
88And
ESR / 293
N
[C20H6BrMnN4O11Re2] •−
Mn(CO)5
•
185,187
95Van
Re: 2.4
Br: 0.9
55
Mn: 0.9
electrochemistry, UV-VIS and IR spectroscopy and
spectroelectrochemistry
[C20H18Mn2N2O4] •−
•−
N
THF
ESR / 293
N
Re(CO)4
(CO)2Cp'Mn
1.9990
79,81
Re(CO)3
N
N
N
electrochemically generated
N
MnCp'(CO)2
reduction with potassium
metal
THF
1.9997
84Gro
55
Mn: 0.747 (2 Mn)
H: 0.227 (4 H)
14
N: 0.865 (2 N)
ESR / RT
electrochemistry, UV-VIS, IR and NMR spectroscopy
reduction with potassium
metal
THF
ESR / 298
1.9997
86Gro
55
87Gro
Mn: 0.750
H: 0.226
14
N: 0.863
electrochemistry, UV-VIS, IR and NMR spectroscopy
Landolt-Börnstein
New Series II/26A2
134
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C20H26O6Re] •
photolysis
2.0046
96Har
benzene
185,187
tBu
•
O
Re(CO)3[OC(CH3)2]
Re: 1.11
ESR / RT
O
tBu
[C20H29O8PRe] •
tBu
•
O
Re(CO)3[P(OCH3)3]
O
photolysis
2.0020
benzene
185,187
96Har
Re: 3.51
P: 2.92
31
ESR / RT
tBu
[C20H35MnN2O10P3] •
•
N
Mn[P(OMe)3]3CO
reduction with sodium
amalgam
2.0018
THF
31
ESR / 220–260
N
94Bro
55
Mn: 0.676
P: 3.043
14
N: 0.386
H(3): 0.07
H(4): 0.437
H(5): 0.13
H(6): 0.10
electrochemistry, EHMO calculations
[C21H10ClN4O3Re] •−
•
N
N
N
N
electrochemically
generated
dichloromethane
Re(CO)3Cl
ESR / 293
2.00346
99Fee
14
N(9,14): 0.497
H(10,13): 0.149
14
N(4,5): 0.065
H: 0.065
electrochemistry, UV-VIS spectroscopy and
spectroelectrochemistry
[C21H14MnO6] •
in situ photolysis
2.00384
88Wan
55
•
O
benzene
ESR / RT
Mn(CO)4
Mn: 0.5368
H: 0.1688 (3H)
H: 0.0765 (1H)
H: 0.0385 (10H)
O
iPr
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.
[C21H14O6Re] •
in situ photolysis
2.0030
88Ho
benzene
185,187
•
O
135
Re: 2.17
ESR / RT
Re(CO)4
O
iPr
[C21H16MnO6] •
•
O
tBu
tBu
photochemically generated
2.0044
THF
55
86Vlc
Mn: 0.27
ESR / 298
O
Mn(CO)3(THF)
[C21H28MnO6] •
tBu
•
O
Mn(CO)3(THF)
chemical oxidation
2.0044
THF
55
ESR / RT
O
96Har
Mn: 0.37
H: 0.35
tBu
[C21H28O6Re] •
tBu
•
O
Re(CO)3(THF)
O
photolysis
2.0043
THF
185,187
96Har
Re: 0.75
ESR / 295
tBu
[C22H16O6Re] •
•
Me
in situ photolysis
2.0033
benzene
185,187
ESR / RT
O
Me
Me
O
Me
Landolt-Börnstein
New Series II/26A2
Re(CO)4
Re: 2.03
88Ho
136
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C22H17N4O3Re] •+
electrochemically generated
2.0036
98Ber1
acetonitrile
185,187
•+
N
N
Re(CO)3(N
N
Re: 0.90
ESR / 250
N CH3)
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C22H17N4O3Re] •+
•+
N
N
Re(CO)3(N
N CH3)
electrochemically generated
2.0020
acetonitrile
185,187
98Ber1
Re: 1.12
ESR / 250
N
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C22H25MnNO5] •
tBu
•
O
Mn(CO)3(py)
O
chemical oxidation
2.0041
96Har
pyridine
55
86Vlc
ESR / RT
Mn: 0.61
H: 0.32
14
N: 0.20
photolysis
2.0038
96Har
benzene
185,187
91Van
tBu
[C22H25NO5Re] •
tBu
•
O
Re(CO)3py
O
Re: 2.01
ESR / RT
tBu
[C22H26MnN4O2] •
tBu
C
N
N
•
THF
ESR / 220–260
CO
Mn
N
N
CO
reduction with sodium
amalgam
C
tBu
2.0018
94Bro
55
Mn: 0.565
N: 0.379
H(3): 0.08
H(4): 0.448
H(5): 0.12
H(6): 0.12
14
electrochemistry, HMO calculations
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
137
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C22H26MnN4O2] •
reduction with sodium
amalgam
2.0018
94Bro
•
tBu
C
N
N
THF
ESR / 220–260
CO
Mn
N
CO
N
C
tBu
55
Mn: 0.564
N: 0.380
H(3): 0.07
H(4): 0.448
H(5): 0.12
H(6): 0.12
14
electrochemistry, HMO calculations
[C23H25N3O4Re] •
irradiation in the presence
of spin trap
•
CH3
2.0048
88And
185,187
Re: 3.59
THF
ESR / 293
H
N
H
N
Re(CO)3(ONtBu)
CH3
[C23H27F12MnN4O8] •
•
O
F3C
H2N
NH2
O
Mn
O
N
O
O
F3C
NH
O
chemical reaction
g(Mn) = 2.004
acetone
A(Mn) = 9.1–9.3
ESR / 298
gx(NO) = 2.0086
gy(NO) = 2.0062
gz(NO) = 2.0032
O
Ax(NO) = 0.43
Ay(NO) = 0.53
Az(NO) = 3.21
CF3
F3C
85Mor1
O
J = 1.50
[C23H35NO5Re] •
tBu
•
O
Re(CO)3(NEt3)
O
tBu
Landolt-Börnstein
New Series II/26A2
ESR / 233
J = 2.35
photolysis
2.0024
benzene
185,187
ESR / RT
Re: 2.46
96Har
138
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C24H17N6O3Re] •+
electrochemically
generated
g1 = 2.0470
g2 = 2.0033
g3 = 1.9670
98Ber1
•+
N
acetonitrile
N
Re(CO)3 (N
N CH3)
ESR / 110
N
N
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C24H19N3O3Re] •
H3C
H3C
•
Ph
N
N
94Sto1
photolysis
cyclohexane
185,187
Re: 2.330
N: 0.468
H(m-H at pyridine):
0.468
14
ESR / 323
Re(CO)3
N
Ph
IR spectroscopy
[C24H19N4O3Re] •+
•+
electrochemically
generated
2.0028
98Ber1
185,187
Re: 0.92
acetonitrile
N
Re(CO)3 (N
N CH3)
N
ESR / 250
electrochemistry, UV-VIS and IR spectroelectrochemistry
[C24H25MnNO6] •
•
OH
tBu
chemical reaction
2.0016
THF
55
89Pro
Mn: 1.13
N: 0.76
14
tBu
ESR / 293
N
Mn(CO)4
O
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
139
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C24H25NO6Re] •
chemical reaction
2.014
89Pro
THF
185,187
•
OH
tBu
Re: 4.00
N: 0.8
14
tBu
ESR / 293
N
Re(CO)4
O
[C25H22F12MnN3O7] •
•
F3C
N
O
chemical reaction
g(Mn) = 2.004
acetone
A(Mn) = 9.1–9.3
ESR / 298
gx(NO) = 2.0086
gy(NO) = 2.0062
gz(NO) = 2.0032
N O
N
Mn
O
O
Ax(NO) = 0.43
Ay(NO) = 0.53
Az(NO) = 3.21
O
F3C
CF3
O
F3C
O
J = 2.14
[C25H35MnN2O3P] •
•
PBu3
N
ESR / 233
J = 3.74
reduction with sodium
amalgam
2.0018
THF
CO
Mn
ESR / 220–260
N
85Mor1
CO
CO
94Bro
55
Mn: 0.18
P: 2.55
14
N: 0.355
H(3): 0.075
H(4): 0.42
H(5): 0.11
H(6): 0.11
31
electrochemistry, EHMO calculations
[C26H18Cl2N4O8Re2] •−
H3C
Ph N
Re(CO)3Cl
N
N Ph
•
chemical reduction
2.0005
acetone
185,187
99Kle
Re: 1.74
ESR / 298
CH3
N
Re(CO)3Cl
electrochemistry, UV-VIS spectroscopy, spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
140
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C26H35MnN5O] •
reduction with sodium
amalgam
2.0018
94Bro
THF
14
CO
N
N
C
•
tBu
ESR / 220–260
Mn
N
N
N
C
tBu
C
tBu
•
tBu
C
N
reduction with sodium
amalgam
2.0018
THF
14
ESR / 220–260
CO
Mn
N
N
N
C
tBu
C
N
O
O
O
O
F3C
Mn: 0.564
N: 0.378
H(3): 0.074
H(4): 0.446
H(5): 0.125
H(6): 0.107
chemical reaction
g(Mn) = 2.004
acetone
A(Mn) = 9.1–9.3
ESR / 298
gx(NO) = 2.0086
gy(NO) = 2.0062
gz(NO) = 2.0032
H
N
N
Mn
F3C
55
electrochemistry, EHMO calculations
•
O
94Bro
tBu
[C27H25F12MnN4O8] •
F3C
Mn: 0.567
N: 0.379
H(3): 0.09
H(4): 0.449
H(5): 0.11
H(6): 0.11
electrochemistry, EHMO calculations
[C26H35MnN5O] •
N
55
O
CF3
N
O
85Mor1
Ax(NO) = 0.43
Ay(NO) = 0.53
Az(NO) = 3.21
O
J < 0.21
data available for toluene / acetone 90.5 / 0.5 at 93 K
[C27H25MnO5P] •
•
O
THF
92Reb
55
Mn: 0.640
P: 2.475
H(3): 1.020
H(4): 1.020
31
Mn(CO)3PPh3
O
photochemical reaction
ESR / 393
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
141
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C28H27F12MnN4O8] •
chemical reaction
g(Mn) = 2.004
85Mor1
acetone
A(Mn) = 9.1–9.3
ESR / 298
gx(NO) = 2.0086
gy(NO) = 2.0062
gz(NO) = 2.0032
•
F3C
N
O
H
N
N
Mn
O
O
O
O
F3C
N
Ax(NO) = 0.43
Ay(NO) = 0.53
Az(NO) = 3.21
O
CF3
O
F3C
O
J < 0.1
ESR / 233
J < 0.16
data available for toluene / acetone 90.5 / 0.5 at 93 K
[C28H34Mn2N2O4] •−
•−
(CO)2Cp*Mn
N
N
MnCp*(CO)2
reduction with potassium
metal
THF
ESR / 298
1.9994
86Gro
55
Mn: 0.763
H: 0.228
14
N: 0.864
NMR, IR and UV-VIS spectroscopy, electrochemistry
[C28H50MnO10P2] •
tBu
•
O
Mn(CO)2[P(OEt3)]2
O
chemical oxidation
2.0039
THF
55
ESR / RT
Mn: 1.60
H: 0.26
31
P: 5.10
chemical oxidation
2.0047
THF
55
96Har
tBu
[C28H50MnO4P2] •
tBu
•
O
Mn(CO)2(PEt3)2
O
96Har
Mn: 2.80
P: 4.95
31
ESR / RT
tBu
[C29H21N4O3PRe] •
•
N
N
electrochemically
generated
THF
Re(CO)3(PPh3)
N
N
ESR / RT
2.0003
185,187
Re: 3.6
P: 3.6
14
N(2): 0.58
H(5): 0.29
31
electrochemistry, IR spectroscopy
Landolt-Börnstein
New Series II/26A2
96Kle
142
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C29H21N4O3PRe] •
electrochemically generated
2.0007
96Kle
THF
185,187
•
N
Re: 2.1
P: 2.1
31
N
ESR / RT
Re(CO)3(PPh3)
N
N
electrochemistry, IR spectroscopy
[C29H21N4O3PRe] •
•
N
N
electrochemically generated
2.0010
THF
185,187
ESR / RT
N
electrochemistry, IR spectroscopy
[C29H21N4O3PRe] •
•
N
Re: 3.1
P: 3.1
14
N(1): 0.5
H(5): 0.5
31
Re(CO)3(PPh3)
N
96Kle
N
electrochemically generated
2.0010
THF
185,187
96Kle
Re: 2.8
P: 2.8
31
ESR / RT
Re(CO)3(PPh3)
N
N
electrochemistry, IR spectroscopy
[C29H32MnO5] •
•
O
tBu
photochemically generated
2.0050
toluene
55
91Van
Mn: 0.096
N: 0.048
14
tBu
ESR / 295
THF
O
Mn(CO)3bpy
55
Mn: 0.056
14
ESR / 295
N: 0.050
IR spectroscopy
[C29H33N2O3PReS] •
•
tBu
N
S
Re(CO)3(PPh3)
N
tBu
electrochemically generated
2.0014
THF
185,187
96Kle
Re: 1.53
P: 4.18
14
N: 0.68
31
ESR / RT
electrochemistry, IR spectroscopy
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.
[C29H47O5PRe] •
photolysis
2.0023
96Har
benzene
185,187
tBu
•
O
143
Re: 4.04
P: 2.69
31
Re(CO)3(PBu3)
ESR / RT
O
tBu
[C31H22ClN8O3ReRu] •+
•+
N
N
electrochemically generated
1.9953
1,2-dichloroethane
185,187
91Mat1
Re: 1.05
ESR / RT
Re(CO)3Cl
(bpy)2Ru
N
N
electrochemistry, UV-VIS spectroscopy
[C31H23N2O3PRe] •
•
electrochemically generated
2.0018
THF
185,187
96Kle
Re: 2.0
P: 2.0
31
N
ESR / RT
Re(CO)3(PPh3)
N
electrochemistry, IR spectroscopy
[C31H27N4O3PRe] •2+
H3C N
(CO)3PPh3
Re
N
N
N CH3
[C31H31MnO5P] •
•
•2+
electrochemically generated
2.0013
94Mat
acetonitrile
185,187
Re: 0.9
P: 0.9
14
N(1): 0.34
H(CH3): 0.34
H(2): < 0.08
N(3): 0.17
H(5): 0.17
H(6): 0.22
90Mat1
photochemical reaction
species 1:
92Reb
toluene
55
31
ESR / 300
Mn: 0.420
P: 1.415
H(1): 0.012
H(4): 0.221
H(5): 0.298
H(6): 0.281
H(7): 0.064
31
O
O Mn(CO)3PPh3
(continued)
Landolt-Börnstein
New Series II/26A2
ESR / 253
144
3.8 Complexes of group 7 (Mn, Tc, Re)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C31H31MnO5P] • (continued)
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
species 2:
55
Mn: 0.420
P: 1.465
H(1): 0.012
H(4): 0.281
H(5): 0.333
H(6): 0.321
H(7): 0.064
31
[C31H35N2O3PRe] •
•
tBu
N
Re(CO)3(PPh3)
N
tBu
electrochemically
generated
2.0013
THF
31
96Kle
185,187
ESR / RT
Re: 4.07
P: 4.07
14
N: 0.72
H: 0.44
photolysis
2.0047
benzene
185,187
88And
Re: 3.973
P: 3.973
14
N: 0.740
H: 0.445
31
ESR / RT
electrochemistry, IR spectroscopy
[C31H35N2O6PRe] •
•
tBu
N
chemical reaction
2.0074
benzene
185,187
ESR / 293
Re: 4.115
P: 3.455
14
N: 0.717
H(imine): 0.435
photolysis
2.0006
benzene
185,187
88And
31
Re(CO)3P(OPh)3
N
tBu
[C31H35O5PRe] •
tBu
•
O
Re(CO)3(PPh2Et)
O
96Har
Re: 3.90
P: 2.60
31
ESR / RT
tBu
[C31H53MnN3O4] •2+
N
• 2+
CH3
O tBu
H3C N
Mn
N
O
electrochemically
generated
gx = gy = 2.05
dichloromethane
ax (Mn) = ay (Mn) = 8.56
az (Mn) = 22.46
E / D = 0.33
ESR / 4
00Mül
gz = 1.85
tBu
O
MeO
electrochemistry, UV-VIS spectroscopy, resonance Raman
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C32H39MnNO6] •
chemical reaction
•
tBu
toluene
ESR / 298
Mn(CO)4
N
O
tBu
Ref. /
add. Ref.
89Kar
55
Mn: 0.78
N: 0.90
H(3): 0.30
H(7): 0.34
H(9): 0.21
tBu
[C32H39NO6Re] •
chemical reaction
•
tBu
toluene
O
89Kar
14
N: 0.85
ESR / 298
Re(CO)4
tBu
g-Factor /
a-Value [mT]
14
O
tBu
145
N
O
tBu
tBu
[C33H21MoN7O7PRe] •
Mo(CO)4
N
N
N
•
O
1,2-dichloroethane
31
irradiation of precursor in
the presence of ligand
•
Ph2
P
Mn(CO)4
P
Ph2
185,187
Re: 1.7
P: 1.7
95Mey
31
P: 1.025
THF
ESR / 298
IR spectroscopy, electrochemistry
[C33H35MnO5P] •
•
photochemical reaction
species 1:
toluene
55
Mn: 0.431
P: 1.648
H(1): 0.012
H(4): 0.226
H(5): 0.298
H(6): 0.271
H(7): 0.064
31
O
O Mn(CO)3[PPh(CH2Ph)2]
(continued)
Landolt-Börnstein
New Series II/26A2
91Mat1
electrochemistry, UV-VIS spectroscopy, luminescence
[C33H23MnNO6P2] •
H3C N
2.0022
ESR / 298
N
Re(CO)3PPh3
O
electrochemical
generation
ESR / 253
92Reb
146
3.8 Complexes of group 7 (Mn, Tc, Re)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C33H35MnO5P] • (continued)
g-Factor /
a-Value [mT]
[Ref. p. 329
Ref. /
add. Ref.
species 2:
55
Mn: 0.431
P: 1.695
H(1): 0.012
H(4): 0.271
H(5): 0.330
H(6): 0.305
H(7): 0.064
31
[C35H22BrMnO5P] •
in situ photolysis
2.00439
88Wan
55
benzene
•
O
ESR / RT
Mn(CO)3PPh3
Mn: 0.8125
P: 2.565
H: 0.1504 (3H)
H: 0.0336 (4H)
31
O
NO2
[C35H22BrO5PRe] •
•
in situ photolysis
2.0024
benzene
185,187
88Ho
Re: 3.07
P: 1.91
31
ESR / RT
O
O
Re(CO)3(PPh3)
Br
[C35H22ClMnO5P] •
in situ photolysis
2.00364
88Wan
55
•
O
benzene
ESR / RT
Mn(CO)3PPh3
Mn: 0.8020
31
P: 2.597
H: 0.1529 (3H)
H: 0.0266 (4H)
O
Cl
[C35H22ClO5PRe] •
•
in situ photolysis
2.0020
benzene
185,187
88Ho
Re: 3.08
P: 1.94
31
ESR / RT
O
O
Re(CO)3(PPh3)
Cl
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
147
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C35H22MnNO7P] •
in situ photolysis
2.00358
88Wan
55
benzene
•
O
ESR / RT
Mn(CO)3PPh3
Mn: 0.8850
P: 2.650
H: 0.1528 (4H)
H: 0.0289 (3H)
31
O
NO2
[C35H22MnNO7P] •
in situ photolysis
2.00350
88Wan
55
•
O
benzene
ESR / RT
Mn(CO)3PPh3
O2N
Mn: 0.8776
P: 2.689
H: 0.1435 (4H)
H: 0.0256 (3H)
31
O
[C35H22NO7PRe] •
•
in situ photolysis
2.0014
benzene
185,187
88Ho
Re: 3.33
P: 2.02
31
O
O2N
O
ESR / RT
Re(CO)3(PPh3)
[C35H22NO7PRe] •
•
in situ photolysis
2.0014
benzene
185,187
88Ho
Re: 3.36
P: 1.98
31
ESR / RT
O
O
Re(CO)3(PPh3)
NO2
[C35H23MnO5P] •
in situ photolysis
2.00361
55
•
O
ESR / RT
Mn(CO)3PPh3
O
Landolt-Börnstein
New Series II/26A2
benzene
Mn: 0.7775
P: 2.568
H: 0.1563 (4H)
H: 0.0342 (4H)
31
88Wan
148
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C35H23O5PRe] •
in situ photolysis
2.0018
88Ho
•
Me
185,187
benzene
Re: 3.00
P: 1.90
31
ESR / RT
O
Me
Me
Re(CO)3(PPh3)
O
Me
[C35H35AsO5Re] •
tBu
•
O
Re(CO)3(AsPh3)
tBu
[C35H35MnO5P] •
•
O
Mn(CO)3(PPh3)
O
tBu
2.0010
benzene
185,187
ESR / RT
O
tBu
photolysis
2.0006
dichloromethane
185,187
ESR / RT
Re: 3.49
As: 3.57
H: 0.3
chemical oxidation
2.0029
dichloromethane
55
ESR / 295
Mn: 1.0
P: 3.35
H: 0.32
chemical oxidation
2.0029
THF
55
95Har
31
ESR / RT
Mn: 0.99
H: 0.33
31
P: 3.36
chemical oxidation
2.0029
dichloromethane
55
toluene
96Har
Mn: 0.99
H: 0.32
31
P: 3.44
photochemical reaction
•
tBu
Re: 3.30
As: 3.30
photolysis
ESR / RT
[C35H35MnO5P] •
96Har
92Reb
55
Mn: 1.00
P: 3.64
H(3): 0.30
H(4): 0.30
31
O
ESR / 293
Mn(CO)3PPh3
O
tBu
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
149
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C35H35O5PRe] •
photolysis
2.0006
96Har
benzene
185,187
92Har
tBu
•
O
Re: 3.82
P: 2.50
31
Re(CO)3(PPh3)
ESR / RT
O
tBu
[C35H35O6PRe] •
tBu
•
O
Re(CO)3(OPPh3)
photolysis
2.0045
benzene
185,187
96Har
Re: 0.8
ESR / RT
O
tBu
[C35H35O8PRe] •
tBu
•
O
Re(CO)3[P(OPh)3]
O
tBu
photolysis
2.0013
benzene
185,187
96Har
Re: 3.44
P: 3.05
31
ESR / RT
photolysis
2.0012
dichloromethane
185,187
Re: 3.36
P: 3.33
31
ESR / RT
[C35H35SbO5Re] •
tBu
•
O
Re(CO)3(SbPh3)
O
photolysis
2.0037
benzene
185,187
ESR / RT
Re: 3.75
Sb: 9.37
123
Sb: 5.10
electrochemically
generated
gx = gy = 2.05
gz = 1.85
dichloromethane
ax (Mn) = ay (Mn) = 9.63
az (Mn) = 22.46
E / D = 0.33
96Har
121
tBu
[C35H45MnN3O4] •2+
N
• 2+
CH3
O Ph
H3C N
ESR / 4
Mn
O
N
00Mül
Ph
O
tBu
MeO
electrochemistry, UV-VIS spectroscopy, resonance Raman
[C35H53O5PRe] •
tBu
•
O
Re(CO)3PCy3
O
tBu
Landolt-Börnstein
New Series II/26A2
photolysis
2.0016
benzene
185,187
Re: 4.09
P: 2.33
31
ESR / RT
96Har
150
3.8 Complexes of group 7 (Mn, Tc, Re)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C36H22MnNO5P] •
in situ photolysis
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.00341
88Wan
55
benzene
•
O
ESR / RT
Mn(CO)3PPh3
Mn: 0.8825
P: 2.683
H: 0.1435 (3H)
H: 0.0233 (2H)
31
O
NC
[C36H22NO5PRe] •
•
in situ photolysis
2.0015
benzene
185,187
88Ho
Re: 3.36
P: 1.99
31
O
O
ESR / RT
Re(CO)3(PPh3)
NC
[C36H25MnO6P] •
in situ photolysis
2.00341
88Wan
55
•
O
ESR / RT
Mn: 0.7226
P: 2.425
H: 0.1601 (3H)
H: 0.0388 (2H)
H: 0.0184 (5H)
in situ photolysis
2.0018
benzene
185,187
benzene
Mn(CO)3PPh3
O
31
H3CO
[C36H25O6PRe] •
•
88Ho
Re: 2.76
P: 1.81
31
O
O
ESR / RT
Re(CO)3(PPh3)
MeO
[C36H26N3O3PRe] •
•
electrochemically
generated
THF
N
N
2.0018
96Kle
185,187
Re: 2.0
P: 2.0
31
ESR / RT
Re(CO)3(PPh 3)
N
electrochemistry, IR spectroscopy
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C36H46N3O3PRe] •
photolysis
H3C
toluene
ESR / 293
Re(PBu3)(CO)3
N
N
94Sto1
Re: 2.730
P: 3.010
14
N: 0.445
H(m-H at pyridine): 0.445
31
IR spectroscopy
[C36H62MnN2O2P2] •
reduction with sodium
amalgam
•
PBu3
THF
CO
Mn
ESR / 220–260
N
Ref. /
add. Ref.
Ph
CH3
N
g-Factor /
a-Value [mT]
185,187
•
Ph
N
151
CO
PBu3
2.0018
94Bro
55
Mn: 0.196
P: 2.36
14
N: 0.345
H(3): 0.072
H(4): 0.43
H(5): 0.12
H(6): 0.12
31
electrochemistry, EHMO calculations
[C36H70MnO4P2] •
•
photochemical reaction
species 1:
toluene
55
92Reb
Mn: 0.583
P: 1.782
H(1): 0.014
H(4): 0.236
H(5): 0.291
H(6): 0.275
H(7): 0.057
31
O
O Mn(CO)2(PBu3)2
ESR / 233
species 2:
31
P: 1.885
[C38H29MnO5P] •
in situ photolysis
2.00381
55
•
O
ESR / RT
Mn(CO)3PPh3
O
iPr
Landolt-Börnstein
New Series II/26A2
benzene
Mn: 0.7558
P: 2.498
H: 0.1560 (3H)
H: 0.0385 (4H)
31
88Wan
152
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
g-Factor /
Solvent / Method / T [K] a-Value [mT]
Ref. /
add. Ref.
[C38H29O5PRe] •
in situ photolysis
2.0018
88Ho
benzene
185,187
•
Re: 2.89
P: 1.88
31
ESR / RT
O
Re(CO)3(PPh3)
O
iPr
[C39H31O5PRe] •
•
Me
in situ photolysis
2.0020
benzene
185,187
88Ho
Re: 2.73
P: 2.04
31
ESR / RT
O
Me
Me
O
Re(CO)3(PPh3)
Me
[C42H34N3O3PRe] •
H3C
photolysis
•
Ph
N
toluene
ESR / 293
Re(PPh3)(CO)3
N
N
94Sto1
185,187
Re: 2.678
P: 3.157
14
N: 0.446
H(m-H at pyridine): 0.446
31
Ph
CH3
IR spectroscopy
[C43H44O5P2Re] •
tBu
•
O
Re(CO)3[Ph2P(CH2)2PPh2]
O
photolysis
2.0009
benzene
185,187
96Har
Re: 3.76
P: 2.50
31
ESR / RT
tBu
[C47H36ClCuN4O3P2Re] •
Cu(PPh3)2
N
N
N
N
Re(CO)3Cl
•
electrochemical
generation
2.0010
91Mat1
185,187
Re: 1.1
1,2-dichloroethane
ESR / 298
electrochemistry, UV-VIS spectroscopy, luminescence
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
153
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H46MnO4P2] •
photochemical reaction
species 1:
92Reb
toluene
55
•
Mn: 0.529
P: 1.339
H(1): 0.014
H(4): 0.242
H(5): 0.330
H(6): 0.283
H(7): 0.064
31
ESR / 233
O
O Mn(CO)2(PPh3)2
species 2:
31
P: 1.377
[C49H37N8O3PReRu] •+
•+
N
N
N
N
electrochemically generated
1.9944
1,2-dichloroethane
185,187
91Mat1
Re: 1.9
P: 1.7
31
Re(CO)3PPh3
(bpy)2Ru
[C50H50MnO4P2] •
photochemical reaction
•
tBu
92Reb
55
ESR / 293
Mn: 2.210
P: 4.645
H(3): 0.225
H(4): 0.225
electrochemical generation
4–7 weak features
toluene
31
O
Mn(CO)2(PPh3)2
O
tBu
[C51H81MnN6] •2+
• 2+
tBu
00Pen
dichloromethane
ESR / 10
N
tBu
N
tBu
N
H
Mn
tBu
NH
NH
N
tBu
tBu
further oxidation yields
[C51H81MnN6]
2•3+
1.965
55
Mn: 7.5
crystal structure, electrochemistry, spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
154
3.8 Complexes of group 7 (Mn, Tc, Re)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C52H37BrMnO4P2] •
in situ photolysis
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.00347
88Wan
55
•
O
ESR / RT
Mn: 1.458
P: 3.185
H: 0.1352 (3 H)
in situ photolysis
1.9990
benzene
185,187
benzene
31
Mn(CO)2(PPh3)2
O
Br
[C52H37BrO4P2Re] •
•
88Ho
Re: 4.48
P: 2.23
31
ESR / RT
O
O
Re(CO)2(PPh3)2
Br
[C52H37ClMnO4P2] •
in situ photolysis
2.00286
88Wan
55
•
O
ESR / RT
Mn: 1.453
P: 3.151
H: 0.1344 (3 H)
in situ photolysis
1.9990
benzene
185,187
benzene
31
Mn(CO)2(PPh3)2
O
Cl
[C52H37ClO4P2Re] •
•
88Ho
Re: 4.703
P: 2.25
31
ESR / RT
O
O
Re(CO)2(PPh3)2
Cl
[C52H37MnNO6P2] •
in situ photolysis
2.00289
88Wan
55
•
O
benzene
ESR / RT
Mn: 1.696
P: 3.438
H: 0.1235 (4H)
31
Mn(CO)2(PPh3)2
O
NO2
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
Substance
Generation / Matrix or
Solvent / Method / T [K]
[C52H37MnNO6P2]•
in situ photolysis
155
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.00301
88Wan
55
•
O
ESR / RT
Mn: 1.655
P: 3.388
H: 0.1175 (4H)
in situ photolysis
1.9986
benzene
185,187
benzene
31
Mn(CO)2(PPh3)2
O2N
O
[C52H37NO6P2Re] •
•
88Ho
Re: 4.30
P: 2.23
31
O
O2N
O
ESR / RT
Re(CO)2(PPh3)2
[C52H37NO6P2Re] •
•
in situ photolysis
1.9994
benzene
185,187
88Ho
Re: 4.24
P: 2.25
31
ESR / RT
O
O
Re(CO)2(PPh3)2
NO2
[C52H38MnO4P2] •
in situ photolysis
2.00298
88Wan
55
ESR / RT
Mn: 1.359
P: 3.083
H: 0.1354 (4 H)
in situ photolysis
1.9991
benzene
185,187
benzene
•
O
31
Mn(CO)2(PPh3)2
O
[C52H38O4P2Re] •
•
88Ho
Re: 4.48
P: 2.23
31
O
ESR / RT
Re(CO)2(PPh3)2
O
[C52H50As2O4Re] •
tBu
•
O
Re(CO)2(AsPh3)2
O
tBu
Landolt-Börnstein
New Series II/26A2
photolysis
1.9956
CH2Cl2
185,187
ESR / RT
Re: 5.23
As: 3.50
75
96Har
156
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C52H50MnO10P2] •
chemical oxidation
2.0034
96Har
THF
55
tBu
•
O
Mn(CO)2[P(OPh)3]2
O
ESR / RT
Mn: 1.15
H: 0.28
31
P: 4.45
chemical oxidation
2.0022
THF
55
tBu
[C52H50MnO4P2] •
tBu
•
O
Mn(CO)2(PPh3)2
O
tBu
ESR / RT
Mn: 1.83
H: 0.30
31
P: 4.21
chemical oxidation
2.0022
dichloromethane
55
ESR / RT
[C52H50O10P2Re] •
tBu
•
O
96Har
Mn: 1.79
H: 0.32
31
P: 3.94
photolysis
1.9995
benzene
185,187
96Har
Re: 4.20
P: 3.33
31
Re(CO)2[P(OPh)3]2
ESR / RT
O
tBu
[C52H50O4P2Re] •
tBu
•
O
photolysis
1.9962
benzene
185,187
96Har
Re: 5.98
P: 2.94
31
Re(CO)2(PPh3)2
ESR / RT
O
tBu
[C53H37MnNO4P2] •
in situ photolysis
2.00295
88Wan
55
•
O
benzene
ESR / RT
Mn: 1.713
P: 3.411
H: 0.1220 (3 H)
31
Mn(CO)2(PPh3)2
O
NC
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
157
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C53H37NO4P2Re] •
in situ photolysis
1.9982
88Ho
benzene
185,187
•
Re: 4.50
P: 2.33
31
O
ESR / RT
Re(CO)2(PPh3)2
O
NC
[C53H40MnO5P2] •
in situ photolysis
2.00272
88Wan
55
•
O
ESR / RT
Mn: 1.222
P: 2.915
H: 0.1395 (3 H)
in situ photolysis
1.9993
benzene
185,187
benzene
31
Mn(CO)2(PPh3)2
O
H3CO
[C53H40O5P2Re] •
•
88Ho
Re: 4.07
P: 2.09
31
O
ESR / RT
Re(CO)2(PPh3)2
O
MeO
[C55H44MnO4P2] •
in situ photolysis
2.00260
88Wan
55
•
O
ESR / RT
Mn: 1.278
P: 3.018
H: 0.1435 (3 H)
in situ photolysis
1.9994
benzene
185,187
benzene
31
Mn(CO)2(PPh3)2
O
iPr
[C55H44O4P2Re] •
•
Re: 4.28
P: 2.20
31
O
O
iPr
Landolt-Börnstein
New Series II/26A2
ESR / RT
Re(CO)2(PPh3)2
88Ho
158
3.8 Complexes of group 7 (Mn, Tc, Re)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C56H46O4P2Re] •
in situ photolysis
1.9979
88Ho
benzene
185,187
•
Me
Re: 3.96
P: 2.42
31
ESR / RT
O
Me
Me
Re(CO)2(PPh3)2
O
Me
[C65H51CuN4O3P3Re] •+
•+
Cu(PPh3)2
N
N
N
electrochemical generation
2.0009
1,2-dichloroethane
185,187
91Mat1
Re: 1.9
P: 2.1
31
ESR / 298
N
Re(CO)3PPh3
electrochemistry, UV-VIS spectroscopy, luminescence
[C76H44FeMnN13] •+
chemical oxidation
[(TPP)Mn-N-Fe(Pc)] •+
THF
2.003
01Don
ESR / 78
IR, Mössbauer and Raman spectroscopy
[C76H88MnN4O4] •
tBu O
•
tBu
air oxidation
2.0088
basic dichloromethane
14
88Mil
N: 0.111
ESR / 298
tBu
-
O
N
Mn N
N
N
tBu
tBu
OtBu
tBu
-
O
tBu
electrochemistry, UV-VIS spectroscopy
Landolt-Börnstein
New Series II/26A2