00200026a2_13.pdf

244
3.12 Complexes of group 11 (Cu, Ag, Au)
Substance
Generation / Matrix or
Solvent / Method / T [K]
[Ref. p. 329
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
2.010
90Mat2
3.12 Complexes of group 11 (Cu, Ag, Au)
[C6AuS10] •
chemical reaction
•
S
S
S
S
S
S
S
S
Au
S
powder spectra
ESR / 77
S
cation [Fe(cp)2]0.25
2.008
powder spectra
ESR / 77
electrochemistry, binding energies
[C6AuSe10] •
chemical reaction
•
Se Se
Au
Se Se
Se
Se
Se
powder spectra
Se
g⊥ = 2.020
g|| = 1.954
90Mat2
ESR / 77
Se
Se
cation [Fe(cp)2]0.2
powder spectra
g⊥ = 2.025
g|| = 1.956
ESR / 77
electrochemistry, binding energies
[C6H6CuMu] •+
muon (Mu, µ) irradiation
•+
Mu
H
ESR / 433
Cu
[C19H20CuF12NO6]•n
O
O
O
F3C
O
•
H3C CH3
CF3
H
O
Cu: 5.75
H(methylene): 4.48
µ: 5.71
polycrystalline powder
gx = 2.05
gy = 2.03
gz = 2.15
ESR / 298
D = 0.16 cm–1
chemical reaction
CF3
H3C CH3
Cu O N
98Sto
63,65
zeolite
F3C
2.0093
84Ben
E / D ≅ 1/3
single crystal
n
g and D tensors
ESR / RT, 4
magnetic data
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
245
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C20H21CuF12N2O6]•n
chemical reaction
g1 = 2.14
g2 = 2.06
g3 = 2.03
92Can1
•
CF3
F3C
O
O
N O Cu
O N
O
ESR / 298
O
F3C
CF3
crystal structure, magnetic measurements
n
[C20H23CuF12N2O6]•n
chemical reaction
•
CF 3
F 3C
O
O N
polycrystalline powder and
single crystal
polycrystalline powder
g⊥ = 2.05
g|| = 2.15
O
ESR / 298
O
single crystal
2.0 (radical)
ESR / 298
g1 = 2.30 (copper)
g2 = 2.10
g3 = 2.06
90Cab
Cu
N O
O
F 3C
CF 3 n
g tensors
crystal structure, magnetic data
[C20H34CuO2S2] •
chemical reaction
•
O
Cu
tBu
THF
CH2CH3
tBu
S
ESR / 295
2.0093
94Ral
63
Cu: 1.206
Cu: 1.291
H: 0.32
65
S
O
CH2CH3
[C21H26CuN2O2S] •
H3C N
•
CH3
O
S
Cu
N O
CH3
toluene
tBu
•
OMe
O
Cu
H3C N
N
Landolt-Börnstein
New Series II/26A2
temperature dependent
equilibrium with CuII redox
isomer
toluene
O
tBu
2.0048
99Ral
63
Cu: 0.51
Cu: 0.54
H(1 H): 0.34
65
ESR / 370
[C21H26CuN2O3S] •
H3C
S
temperature dependent
equilibrium with CuII redox
isomer
ESR / 370
2.0046
63
Cu: 0.41
Cu: 0.44
H(1 H): 0.34
65
99Ral
246
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C21H34CuO2S3] •
chemical reaction
2.0058
94Ral
THF
63,65
S
•
tBu
O
Cu
S
ESR / 295
S
O
tBu
[C22H36CuO2S2] •
•
S
tBu
O
O
2.0066
THF
63
94Ral
ESR / 295
Cu: 1.059
Cu: 1.135
H: 0.32
chemical reaction
D = 0.043 cm–1
97Osh
ethanol
E = 0.014 cm–1
95Osh
tBu
[C24H32AgN6O2] 2•+
2•+
N
ESR / 5
Ag
N
chemical reaction
65
Cu
S
Cu: 1.17
H: 0.33
N
O
2
crystal structure, magnetic susceptibility , electrochemistry, UVVIS spectroscopy
[C24H32CuN2O2S] •
•
CH3
tBu
O
chemical reaction
2.0052
97Ral
THF
63
Cu: 0.51
Cu: 0.54
H(4): 0.30
99Ral
2.0055
99Ral
65
ESR / > 350
S
Cu
tBu
O
N
N CH3
[C24H32CuN2O2S] •
•
CH3
tBu
O
S
toluene
Cu
O
tBu
N
temperature dependent
equilibrium with CuII redox
isomer
N CH3
63
Cu: 0.53
Cu: 0.56
H(4,5): 0.33
65
ESR / 320
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
247
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C24H40CuO2S4] •
chemical reaction
2.0059
94Ral
•
S
S
S
S
tBu
O
Cu
THF
63,65
Cu: 1.21
H: 0.32
ESR / 295
O
tBu
[C25H34CuN2O2S] •
•
H3C
tBu
S
O
Cu
tBu
temperature dependent
equilibrium with CuII redox
isomer
toluene
O
N
2.0054
99Ral
63
Cu: 0.56
Cu: 0.60
H(4): 0.32
65
N CH3
ESR / 380
[C25H34CuN2O3S] •
tBu
CH3
S
O
Cu
N O
H3C N
•
OMe
toluene
tBu
•
tBu
O
OMe
O
OMe
Cu
H3C N
N
tBu
[C26H36CuN6O2] 2•+
2• +
N
Cu
N
N
2.0047
99Ral
63
Cu: 0.41
Cu: 0.44
H(5): 0.36
65
ESR / 330
[C26H36CuN2O4S] •
H3C
S
temperature dependent
equilibrium with CuII redox
isomer
temperature dependent
equilibrium with CuII redox
isomer
2.0047
99Ral
63
Cu: 0.39
Cu: 0.42
65
toluene
ESR / 330
chemical reaction
2.0
97Osh
ethanol
D = 3.6 cm–1
95Osh
ESR / 5
E = 0 cm–1
O
2
crystal structure, magnetic susceptibility, electrochemistry, UVVIS spectroscopy
Landolt-Börnstein
New Series II/26A2
248
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C28H32Cu2N6] •+
electrochemical or chemical
reduction
2.0053
87Kai2
•+
Cu(Cod)
N
N N
N
dichloromethane
ESR / 300
N N
Cu(Cod)
Cu: 0.960
14
N: 0.646
14
N: 0.427
Cod =
electrochemistry
[C28H34CuO2S2] •
•
C6H5
S
Cu
S
O
THF
63
ESR / 295
Cu: 1.128
Cu: 1.208
H: 0.33
chemical reaction
2.08 (broad)
THF
4.34 (broad, weak)
94Ral
tBu
C6H5
[C28H40CuO4] 2•
tBu
2.0087
65
tBu
O
chemical reaction
O
tBu
O
Cu
O
2•
86Tho
ESR / 163
O
tBu
tBu
crystalline solid
2.00
ESR / 163
crystal structure, UV-VIS spectroscopy
[C31H53CuN3O4] •+
N
H3C N
electrochemical generation
•+
CH3
O tBu
dichloromethane
gx = 2.034
gy = 2.021
gz = 2.1
98Mül
ESR / 10
Cu
N
O
tBu
O
tBu
MeO
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
249
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C35H45CuN3O4] •+
electrochemical generation
gx = 2.034
gy = 2.021
gz = 2.1
98Mül
N
•+
CH3
dichloromethane
ESR / 16
O Ph
H3C N
Cu
N
O
Ph
simulated for
effective spin = 1
(strong coupling)
Ax = 2.1
Ay = 2.1
Az = 10.7
O
tBu
MeO
crystal structure, electrochemistry, UV-VIS spectroscopy
[C42H38Cu2N4S2] •−
electrochemically generated 2.0019
•−
THF
95Sta2
63,65
Cu: 0.53
N: 0.29
H: 0.29
14
ESR / RT
CH3
CH3
H3C
S
N
N
Cu
N
Cu
N
S
CH3
H3C
CH3
electrochemistry, UV-VIS spectroscopy
[C42H52Br2CuN2O4] 2•
tBu
chemically generated
2•
O
tBu
chloroform
2.0044
96Kas
H(m, 2H): 0.1123
N(1 N): 0.232
H(NH): 0.232
14
ESR / 300
NH CH
2
Cu
O
Br
2
IR and UV-VIS spectroscopy
[C42H52Cl2CuN2O4] 2•
tBu
chemically generated
2•
O
tBu
chloroform
ESR / 300
Cu
Landolt-Börnstein
New Series II/26A2
Cl
2
H(m, 2H): 0.1143
N(1 N): 0.2286
H(NH): 0.2286
14
NH CH
2
O
2.0038
IR and UV-VIS spectroscopy
96Kas
250
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C42H54CuN2O4] 2•
chemically generated
2.0034
96Kas
2•
O
tBu
chloroform
tBu
H(m, 2H): 0.111
N(1 N): 0.222
H(NH): 0.222
14
ESR / 300
NH CH
2
Cu
O
2
IR and UV-VIS spectroscopy
[C44H20AgCl8N4] •+
electrochemically generated 2.0620
•+
Cl
N
Ag N
N
N
Cl
14
N: 2.3
ESR / 298
Cl
Cl
dichloromethane
91Tun
Cl
dichloromethane
2.0652
ESR / 77
14
N: 2.6
Cl
Cl
Cl
electrochemistry
[C44H20Cl8CuN4] •+
•+
Cl
Cl
Cl
N
N
Cu
N
N
Cl
Cl
Cl
Cl
electrochemically generated g⊥ = 2.0240
g|| = 2.1230
dichloromethane
A⊥ = 1.6
ESR / 298
A|| = 9.2
dichloromethane
ESR / 77
91Tun
g⊥ = 1.9915
g|| = 2.1930
A⊥ = 1.6
A|| = –
Cl
electrochemistry
[C44H28AgN4] •+
[Ag(TPP)] •+
electrochemically generated 2.0628
dichloromethane
91Tun
14
N: 2.2
ESR / 298
dichloromethane
2.0605
ESR / 77
14
N: 2.3
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
251
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C44H28CuN4] •+
electrochemically generated
91Tun
[Cu(TPP)] •+
dichloromethane
g⊥ = 2.0130
g|| = 2.1098
ESR / 298
dichloromethane
ESR / 77
A⊥ = 1.5
A|| = 9.0
g⊥ = 2.0494
g|| = 2.1754
A⊥ = 1.7
A|| = –
electrochemistry
[C44H36CuN4P2] •
•
N
N
Cu
N
electrochemically generated
2.0026
THF
63,65
92Vog1
Cu: 1.44
P: 1.59
14
N(1): 0.44
H(3): < 0.03
14
N(4): 0.12
H(5): 0.32
H(6): < 0.03
31
PPh3
ESR / 295
PPh3
N
electrochemistry, UV-VIS spectroscopy
[C44H38Cu2N2O2P2] •+
chemical reduction
2.0039
89Bes2
63,65
Cu(PPh3)2
N
O
H3C
O
N
CH3
Cu(PPh3)2
[C47H36ClCuN4O3P2Re] •
Cu(PPh3)2
N
N
N
N
Re(CO)3Cl
Landolt-Börnstein
New Series II/26A2
•
•+
dichloromethane
ESR / 298
Cu(2 Cu): 1.06
P(4 P): 0.835
14
N: 0.076
H(3,6): 0.076
H(CH3): 0.305
31
HMO calculations
electrochemical generation
2.0010
1,2-dichloroethane
185,187
Re: 1.1
ESR / 298
electrochemistry, UV-VIS spectroscopy, luminescence
91Mat2
252
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C48H32CuN4] •
electrochemically
generated
g1 = 2.011
g2 = 2.0025
g3 = 1.993
95Sta
•
Ph
THF
N
ESR / 110
Cu
N
2
Ph
electrochemistry, UV-VIS spectroscopy
[C48H40CuN4O2P2] •
H3C
O
N
O Cu(PPh3)2
N
•
electrochemically
generated
2.0038
THF
63
ESR / 298
N N
CH3
00Hor
65
Cu: 1.29
Cu: 1.21
31
P: 1.02
14
N(5): 0.74
14
N(10): 0.28
H(6): 0.28
H(9): 0.28
electrochemistry, NMR and IR spectroscopy, UV-VIS and IR
spectroelectrochemistry
[C50H50AgO2P2] •
chemical reaction
•
tBu
THF
107
Ag: 0.158
Ag: 0.186
31
P: 0.44
H: 0.342
H: 0.058
H(tBu): 0.033
109
O
tBu
88Boc1
O
ENDOR / 180
Ag(PPh3)2
electrochemistry
[C52H38CuN4P2] •
•
N
N
N
N
electrochemically
generated
2.00339
99Fee
14
N(9,14): 0.54
dichloromethane
Cu(PPh3)2
ESR / 293
electrochemistry, UV-VIS spectroscopy and spectroelectrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
253
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C53H42CuN2O8P2] •
electrochemically generated
2.0049
99Wan
dichloromethane
63
•
O
O
H3COOC
N
H
H3COOC
N
Cu(PPh3)2
Cu: 0.64
Cu: 0.71
31
P(2 P): 0.90
14
N(1 N): 0.79
65
ESR / 293
O
OCH3
crystal structure of precursor
[C56H78CuN2O4] •
tBu
•
tBu
chemical reaction
g1 = 1.996 (Cu: 25)
toluene
g2 = 1.973
95Spe
ESR / 77
O
tBu
N
Cu
O
2
crystal structure, magnetic susceptibility, electrochemistry,
UV-VIS spectroscopy
tBu
[C58H62Cu2N2O4P4] •+
•+
O
[C60H54Cu2N4P4] •+
•+
N
Landolt-Börnstein
New Series II/26A2
N
aqueous methanol
63
ESR / 300
Cu: 1.592
Cu: 1.640
14
N: 0.592
31
P: 2.096
electrochemical generation
2.0015
dichloromethane
63
Cu: 0.74
N: 0.213
31
P: 0.97
H(5): 0.500
H(4,6): 0.046
14
ESR / RT
N
Cu(PPh3)2
N
2.0113
91Kai2
65
(PPh2Me)2Cu C OCH2CH3
N N
CH3CH2O C Cu(PPh2Me)2
O
(PPh3)2Cu
chemical reaction
93Vog
254
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C62H70Cu2N2O4P4] •+
chemical reaction
2.0116
91Kai2
aqueous methanol
63
•+
(PPh2Me)2Cu C OtBu
N N
tBuO C Cu(PPh2Me)2
O
[C64H36Cu4F48N6O20]•
•
O
O
Cu
O
N
N
O
O
Cu
O
O
= hfac
Cu
O
O
single crystal
ESR / 4.2
N
O
−
gmax = 2.281
gmin = 2.267
95Lan
amax = 15.3
amin = 3.4
O
N
O
chemical reaction
O
O
O
ESR / 300
Cu: 1.636
Cu: not observed
14
N: 0.636
31
P: 2.016
65
O
O
O
O
O
O
N
N
Cu
O
O
O
O
F3C
CF3
magnetic measurements, specific heat studies
[C64H52CuN8P2Ru] • 2+
• 2+
N
N
N
N
electrochemically generated
1.9952
1,2-dichloroethane
14
91Mat1
N: 0.24
Cu(PPh3)2
(bpy)2Ru
electrochemistry, UV-VIS spectroscopy
[C64H56Cu2N6P4] •+
Ph2
N
P
Cu
N
P
Ph2 N
•+
electrochemical or chemical
reduction
2.0058
dichloromethane
31
ESR / 300
N
N
Ph2
P
Cu
N
87Kai2
63,65
Cu: 0.936
P: 0.780
14
N: 0.624
(coordinating tetrazine
nitrogen)
14
N: 0.442
P
Ph2
electrochemistry
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
255
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C64H62Cu2N4P4] •+
electrochemical
generation
2.0020
93Vog
Ph2
N
P
(CH2)4 Cu
P
N
Ph2
Ph2
N
P
Cu
(CH2)4
P
N
Ph2
[C64H69CuNO2P2] •
•
tBu
•+
dichloromethane
ESR / RT
Cu: 0.70
N: 0.219
31
P: 0.91
H(5): 0.492
H(4,6): 0.040
14
chemical reaction
2.004
toluene
63
95Spe
Cu: 0.99
Cu: 1.06
14
N(1 N): 0.7
31
P(2 P): 1.46
H(3 H): 0.158
65
ESR / 77
O
Cu(PPh3)2
tBu
63
N
O
tBu
crystal structure, magnetic susceptibility, electrochemistry,
UV-VIS spectroscopy
tBu
[C64H70Cu2N2O4P4] •+
PPh2
(CH2)3 Cu O C OtBu
PPh2 N N PPh2
C Cu
(CH2)3
tBuO
O
PPh2
[C65H51CuN4O3P3Re] •+
Cu(PPh3)2
N
N
N
N
Re(CO)3PPh3
•+
•+
chemical reaction
2.0088
aqueous methanol
63
Cu: 1.848
Cu: not observed
14
N: 0.632
31
P: 2.480
65
ESR / 300
electrochemical
generation
1,2-dichloroethane
2.0009
185,187
Re: 1.9
P: 2.1
31
ESR / 298
electrochemistry, UV-VIS spectroscopy, luminescence
Landolt-Börnstein
New Series II/26A2
91Kai2
91Mat2
256
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C66H66Cu2N4P4] •+
electrochemical generation
2.0017
93Vog
dichloromethane
63
Ph2
P
N
(CH2)5 Cu
P
N
Ph2
Ph2
N
P
Cu
(CH2)5
P
N
Ph2
•+
ESR / RT
[C68H66Cu2N2O4P4] •+
•+
O
(PPh2Me)2Cu C OCH2Ph
N N
PhCH2O C Cu(PPh2Me)2
O
Ph2
P
Cu
(CH2)6
P
N
Ph2
N
[C68H78Cu2N2O4P4] •+
•+
crystal structure, electrochemistry, UV-VIS
spectroscopy, NMR
96Sch2
chemical reaction
2.0111
91Kai2
aqueous methanol
63
ESR / 300
Cu: 1.580
Cu: 1.631
14
N: 0.584
31
P: 2.152
electrochemical generation
2.0026
dichloromethane
63
65
[C68H70Cu2N4P4]•+
Ph2
N
P
(CH2)6 Cu
P
N
Ph2
Cu: 0.71
N: 0.213
31
P: 0.92
H(5): 0.467
H(4,6): 0.046
14
•+
93Vog
Cu: 0.79
N: 0.213
31
P: 1.00
H(5): 0.500
H(4,6): 0.046
14
ESR / RT
crystal structure, electrochemistry, UV-VIS
spectroscopy, NMR
96Sch2
chemical reaction
2.0098
91Kai2
aqueous methanol
63
Cu: 1.570
Cu: 1.681
14
N: 0.634
31
P: 1.856
65
Ph2P
OtBu
O
Cu C
Ph2P N N PPh2
C Cu
tBuO
O
PPh2
ESR / 300
electrochemistry and UV-VIS spectroscopy
93Mos
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
257
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C70H72Cu2N4P4] •+
chemical reaction
2.0051
99Bar
dichloromethane
63
•+
(CH2)6
Ph2P
Cu
ESR / 300
Cu: 1.300
Cu: 1.393
31
P: 1.480
acetone / ethanol 5:1
2.0050
65
PPh2
N
N
N
N
Cu
PPh2
Ph2P
high field ESR (245 GHz) / 4 g1: 2.0134
g2: 2.0047
g3: 1.9968
(CH2)6
[C70H82Cu2N2O4P4] •+
(CH2)6
•+
chemical reaction
2.0104
91Kai2
aqueous methanol
63
99Bar
ESR / 300
Cu: 1.652
Cu: 1.769
14
N: 0.640
31
P: 1.856
acetone / ethanol 5:1
2.0110
99Bar
65
Ph2P
O
OtBu
Cu C
Ph2P N N PPh2
C Cu
tBuO
O
PPh2
(CH2)6
high field ESR (245 GHz) / 4 g1: 2.0220
g2: 2.0090
g3: 2.0020
[C72H72Cu2N6P4] •+
chemical reaction
2.0054
99Bar
dichloromethane
63
PPh2
Ph2P
Cu
N N
N
ESR / 300
N N
acetone / ethanol 5:1
2.0055
PPh2
high field ESR (245 GHz) / 4 g1: 2.0070
g2: 2.0070
g3: 2.0024
65
Cu
Ph2P
93Mos
Cu: 0.760
Cu: 0.813
31
P: 0.923
14
N: 0.613
14
N: 0.463
(CH2)6
N
•+
crystal structure, electrochemistry and UV-VIS
spectroscopy
(CH2)6
[C72H78Cu2N4P4] •+
Ph2
N
P
(CH2)8 Cu
P
N
Ph2
Landolt-Börnstein
New Series II/26A2
Ph2
N
P
Cu
(CH2)8
P
N
Ph2
•+
electrochemical generation
2.0020
96Sch2
dichloromethane
63
99Bar
Cu: 0.67
N: 0.213
31
P: 0.90
H: 0.50
14
ESR / RT
crystal structure, electrochemistry, UV-VIS spectroscopy,
NMR
258
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C76H80Cu2N6P4] •+
chemical reaction
2.0054
99Bar
dichloromethane
63
•+
PPh2
Ph2P
Cu
N N
N
ESR / 300
Cu: 0.785
Cu: 0.840
31
P: 0.944
14
N: 0.628
14
N: 0.468
N N
acetone / ethanol 5:1
2.0054
PPh2
high field ESR (245 GHz) / 4 g1: 2.0070
g2: 2.0070
g3: 2.0022
(CH2)8
N
65
Cu
Ph2P
(CH2)8
[C80H64Cl2Cu2N6P4] •+
(PPh3)2Cu
N
N
Cl
Cl
N
N
electrochemically generated
•+
2.0077
98Dos
dichloromethane
ESR / 298
N
N Cu(PPh )
3 2
crystal structure, electrochemistry, UV-VIS spectroscopy
[C80H66Cu2N4P4] •+
•+
N
electrochemically generated
2.0017
dichloromethane
63
ESR / RT
Cu: 0.646
Cu: 0.691
31
P: 0.691
14
N: 0.218
electrochemical generation
2.0032
dichloromethane
63
65
N
Cu(PPh3)2
(PPh3)2Cu
N
91Mat1
N
93Vog
Cu: 0.646
65
[C82H66Cl4Cu2N2O4P4] •+
O
[P(4-ClC6H4)3]2Cu C OtBu
N N
tBuO C Cu[P(4-ClC6H4)3]2
O
•+
Cu: 0.691
P: 0.691
14
N: 0.215
H(5): 0.500
H(4,6): 0.046
ESR / RT
31
electrochemical generation
2.0085
aqueous methanol
ESR / 300
91Kai2
63
Cu: 1.511
Cu: not observed
14
N: 0.613
31
P: 1.570
65
Landolt-Börnstein
New Series II/26A2
Ref. p. 329]
3 Radicals in metal complexes
259
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C82H78Cu2N2O4P4] •+
chemical reaction
2.0102
91Kai2
aqueous methanol
63
O
(PPh3)2Cu C OtBu
N N
tBuO C Cu(PPh3)2
O
•+
ESR / 300
[C84H66Cu2N2O2P4] •+
electrochemistry and UV-VIS spectroscopy
93Mos
ESR / RT
97Ral
•+
N
O
N
O
(PPh3)2Cu
N
Cu: 1.00
P: 1.40
Cu(PPh3)2
•+
O
63,65
31
[C84H66Cu2N2O2P4] •+
(PPh3)2Cu O
Cu: 1.607
Cu: 1.721
14
N: 0.640
31
P: 1.872
65
Cu(PPh3)2
N
+ unresolved fine
structure
electrochemical or chemical
reduction
2.0058
dichloromethane
31
87Kai2
63,65
Cu: 0.643
P: 0.835
ESR / 300
electrochemistry
[C84H68Cu2N6P4] •+
Cu(PPh3)2
N N
N
N
•+
N N
Cu(PPh3)2
electrochemical or chemical
reduction
2.0055
87Kai2
63,65
31
ESR / 300
Cu: 0.758
P: 0.910
14
N: 0.605
14
N: 0.463
99Bar
dichloromethane
acetone / ethanol 5:1
2.0053
99Bar
high field ESR (245 GHz) / 4 g1: 2.0067
g2: 2.0067
g3: 2.0026
electrochemistry
[C92H78Cu2N4P4] •+
H3C
Ph N
Cu(PPh3)2
N
N Ph
N
CH3
Cu(PPh3)2
Landolt-Börnstein
New Series II/26A2
•+
reduction with Bu4NBH4
2.0030
dichloromethane
63,65
99Kle
Cu: 1.32
N: 0.34
14
ESR / 298
electrochemistry, UV-VIS spectroscopy, spectroelectrochemistry
260
3.12 Complexes of group 11 (Cu, Ag, Au)
[Ref. p. 329
Substance
Generation / Matrix or
Solvent / Method / T [K]
g-Factor /
a-Value [mT]
Ref. /
add. Ref.
[C94H102Cu2N2O4P4] •+
chemical reaction
2.0111
91Kai2
aqueous methanol
63
[P(4-CH3C6H4)]2Cu C OtBu
N N
tBuO C Cu[P(4-CH3C6H4)]2
O
ESR / 300
Cu: 1.608
Cu: 1.722
14
N: 0.638
31
P: 1.928
[C100H98Cu2N2O4P4] •+
chemical reaction
2.0107
aqueous methanol
63
O
O
[P(4-CH3C6H4)3]2Cu C OCH2C6H5
N N
C6H5CH2O C Cu[P(4-CH3C6H4)3]2
O
•+
•+
65
91Kai2
Cu: 1.548
Cu: not observed
14
N: 0.608
31
P: 2.104
65
ESR / 300
Landolt-Börnstein
New Series II/26A2