Identifying similarities and differences between
analogous bisdithiolene and bisdiselenolene
complexes: A computational study.
Eric A. C. Bushnell1,2* and Russell J. Boyd2
1
Department of Chemistry, Brandon University, 270-18th Street, Brandon, Manitoba
R7A 6A9, Canada
2
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada, B3H
4R2.
Supplementary Information
(Tables S1 – S14, 10 pages in total)
Table S1. Calculated reduction potentials (in eV) for [M(L')2]0/[M(L')2]1– and
[M(L)2]0/[M(L)2]1– (M = Ni, Pd and Pt) at the IEFPCM-M06/BS1//M06-L/BS1 level of
theory. All values are relative to the calculated value of 4.95 V for Eº(Fc+•/Fc) at the
IEFPCM-M06/BS1//M06-L/BS1 level of theory
[M(1')2]0/[M(1')2]1–
[M(2')2]0/[M(2')2]1–
[M(3')2]0/[M(3')2]1–
[M(4')2]0/[M(4')2]1–
[M(5')2]0/[M(5')2]1–
[M(6')2]0/[M(6')2]1–
1–
2–
[M(1')2] /[M(1')2]
[M(2')2]1–/[M(2')2]2–
[M(3')2]1–/[M(3')2]2–
[M(4')2]1–/[M(4')2]2–
[M(5')2]1–/[M(5')2]2–
[M(6')2]1–/[M(6')2]2–
Ni
-0.61
0.56
0.28
-0.13
0.45
0.30
Pd
-0.59
0.59
0.29
-0.07
0.46
0.30
Pt
-0.76
0.42
0.09
-0.27
0.29
0.12
Ni
-1.56
-0.40
-0.80
-0.96
-0.46
-0.57
Pd
-1.28
-0.30
-0.97
-0.80
-0.35
-0.47
Pt
-1.49
-0.53
-0.95
-1.06
-0.61
-0.73
[M(1)2]0/[M(1)2]1–
[M(2)2]0/[M(2)2]1–
[M(3)2]0/[M(3)2]1–
[M(4)2]0/[M(4)2]1–
[M(5)2]0/[M(5)2]1–
[M(6)2]0/[M(6)2]1–
1–
2–
[M(1)2] /[M(1)2]
[M(2)2]1–/[M(2)2]2–
[M(3)2]1–/[M(3)2]2–
[M(4)2]1–/[M(4)2]2–
[M(5)2]1–/[M(5)2]2–
[M(6)2]1–/[M(6)2]2–
Ni
-0.51
0.61
0.36
0.00
0.47
0.39
Pd
-0.42
0.59
0.38
-0.01
0.44
0.29
Pt
-0.54
0.43
0.12
-0.16
0.24
0.13
Ni
-1.28
-0.37
-0.74
-0.90
-0.51
-0.66
Pd
-1.06
-0.25
-0.56
-0.74
-0.35
-0.45
Pt
-1.33
-0.45
-0.77
-0.94
-0.58
-0.69
Table S2. The contributions (in %) of the various atoms to the redox active b2g MOs for
[M(L')2]0, [M(L')2]1–, [M(L)2]0 and [M(L')2]1–.
C1/C2 2pz
S1/S2 3pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Ni dxz
C1/C2 2pz
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Ni dxz
C1/C2 2pz
S1/S2 3pz
Ni(1')20
Ni(2')20
Ni(3')20
Ni(4')20
Ni(5')20
Ni(6')20
5.20
3.27
4.30
1.85
1.66
0.84
15.89
15.84
15.45
14.14
13.60
13.03
0.00
0.00
0.00
2.33
2.68
2.66
0.00
0.00
0.00
2.10
1.23
3.49
13.46
14.36
14.88
16.24
16.43
17.42
0
0
0
0
0
Ni(1)2
Ni(2)2
Ni(3)2
Ni(4)2
Ni(5)2
Ni(6)20
5.17
2.84
3.43
1.35
1.25
0.42
15.61
16.35
16.67
15.54
14.98
14.43
0.00
0.00
0.00
1.75
2.08
2.20
0.00
0.00
0.00
1.57
0.80
2.67
14.87
15.86
16.50
17.40
17.37
18.92
Ni(1')21–
Ni(2')21–
Ni(3')21–
Ni(4')21–
Ni(5')21–
Ni(6')21–
4.56
2.70
3.36
0.92
0.50
0.00
15.99
16.13
16.58
14.62
13.65
13.64
2
C3/C6(N3/N6) 2pz
C4/C5 2pz
Ni dxz
C1/C2 2pz
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Ni dxz
C1/C2 2pz
S1/S2 3pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pd dxz
C1/C2 2pz
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pd dxz
C1/C2 2pz
S1/S2 3pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pd dxz
C1/C2 2pz
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pd dxz
C1/C2 2pz
S1/S2 3pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pt dxz
C1/C2 2pz
0.00
0.00
15.30
Ni(1)21–
4.12
16.40
0.00
0.00
15.23
0.00
0.00
15.70
Ni(2)21–
2.15
17.33
0.00
0.00
15.60
0.00
0.00
16.54
Ni(3)21–
2.61
17.58
0.00
0.00
16.41
0.00
1.97
16.54
Ni(4)21–
0.69
16.31
2.02
1.51
15.96
3.37
1.27
16.50
Ni(5)21–
0.33
15.70
2.63
1.01
15.99
1.43
1.75
16.77
Ni(6)21–
0.00
14.93
2.39
3.00
16.01
Pd(1')20
6.27
15.17
0.00
0.00
8.55
Pd(1)20
5.48
15.86
0.00
0.00
9.02
Pd(1')21–
5.68
15.26
0.00
0.00
10.98
Pd(1)21–
4.92
15.98
0.00
0.00
11.38
Pd(2')20
3.56
16.30
0.00
0.00
10.23
Pd(2)20
2.85
17.27
0.00
0.00
11.17
Pd(2')21–
3.22
16.29
0.00
0.00
11.64
Pd(2)21–
2.57
17.18
0.00
0.00
13.27
Pd(3')20
4.14
16.80
0.00
0.00
9.66
Pd(3)20
3.51
17.47
0.00
0.00
11.89
Pd(3')21–
2.07
18.51
0.00
0.00
12.34
Pd(3)21–
3.02
17.43
0.00
0.00
14.09
Pd(4')20
1.77
15.54
2.16
2.14
11.36
Pd(4)20
1.36
16.84
1.62
1.54
12.08
Pd(4')21–
1.53
15.49
2.06
1.95
13.17
Pd(4)21–
1.17
16.63
1.47
1.45
14.54
Pd(5')20
1.41
15.04
2.92
0.96
11.70
Pd(5)20
1.07
16.41
2.15
0.67
12.48
Pd(5')21–
1.29
14.91
2.79
0.83
14.36
Pd(5)21–
0.98
16.14
2.04
0.58
15.01
Pd(6')20
0.70
14.53
2.81
3.21
12.43
Pd(6)20
0.37
16.00
2.21
2.45
13.31
Pd(6')21–
0.52
14.23
2.80
2.93
15.13
Pd(6)21–
0.26
15.64
2.20
2.25
15.88
Pt(1')20
5.96
14.55
0.00
0.00
13.28
Pt(1)20
5.18
Pt(2')20
3.38
15.61
0.00
0.00
14.20
Pt(2)20
2.70
Pt(3')20
3.55
16.44
0.00
0.00
14.75
Pt(3)20
3.29
Pt(4')20
1.66
14.83
2.05
2.04
15.69
Pt(4)20
1.28
Pt(5')20
1.34
14.34
2.77
0.90
15.83
Pt(5)20
1.02
Pt(6')20
0.64
13.85
2.68
3.03
16.46
Pt(6)20
0.34
3
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pt dxz
C1/C2 2pz
S1/S2 3pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pt dxz
C1/C2 2pz
Se1/Se2 4pz
C3/C6(N3/N6) 2pz
C4/C5 2pz
Pt dxz
15.14
0.00
0.00
13.60
Pt(1')21–
5.40
14.56
0.00
0.00
16.47
Pt(1)21–
4.64
15.17
0.00
0.00
16.65
16.49
0.00
0.00
14.52
Pt(2')21–
3.04
15.46
0.00
0.00
17.42
Pt(2)21–
2.42
16.27
0.00
0.00
17.54
16.65
0.00
0.00
15.17
Pt(3')21–
3.45
16.18
0.00
0.00
18.07
Pt(3)21–
2.81
16.36
0.00
0.00
18.30
16.01
1.54
1.45
15.81
Pt(4')21–
1.43
14.58
1.94
1.84
19.34
Pt(4)21–
1.10
15.73
1.39
1.37
19.24
15.76
2.06
0.64
16.01
Pt(5')21–
1.22
14.09
2.63
0.98
19.37
Pt(5)21–
0.93
15.37
1.94
0.54
19.32
15.24
2.10
2.33
16.86
Pt(6')21–
0.49
13.47
2.65
2.76
19.98
Pt(6)21–
0.24
14.78
2.08
2.12
20.19
Table S3. Selected average bond lengths for the neutral bisdithiolene- and
bisdiselenolene-Ni complexes
Complex
r(Ni–S)
r(C–S)
r(C=C)
Complex
r(Ni–Se)
r(C–Se)
r(C=C)
Ni(1')20
2.146
1.704
1.384
Ni(1)20
2.270
1.856
1.375
Ni(2')20
2.147
1.701
1.398
Ni(2)20
2.272
1.854
1.388
Ni(3')20
2.138
1.698
1.383
Ni(3)20
2.262
1.853
1.373
Ni(4')20
2.152
1.717
1.419
Ni(4)20
2.277
1.871
1.412
Ni(5')20
2.153
1.712
1.420
Ni(5)20
2.277
1.866
1.414
Ni(6')20
2.158
1.713
1.425
Ni(6)20
2.283
1.869
1.418
Table S4. Selected average bond lengths for the monoanionic bisdithiolene- and
bisdiselenolene-Ni complexes
Complex
r(Ni–S)
r(C–S)
r(C=C)
Complex
r(Ni–Se)
r(C–Se)
r(C=C)
Ni(1')21–
2.179
1.734
1.361
Ni(1)21–
2.303
1.886
1.354
Ni(2')21–
2.169
1.726
1.380
Ni(2)21–
2.296
1.878
1.374
4
Ni(3')21–
2.162
1.726
1.367
Ni(3)21–
2.287
1.880
1.360
Ni(4')21–
2.179
1.738
1.410
Ni(4)21–
2.306
1.893
1.404
Ni(5')21–
2.175
1.728
1.415
Ni(5)21–
2.302
1.882
1.410
Ni(6')21–
2.182
1.730
1.427
Ni(6)21–
2.310
1.887
1.422
Table S5. Selected average bond lengths for the dianionic bisdithiolene- and
bisdiselenolene-Ni complexes
Complex
r(Ni–S)
r(C–S)
r(C=C)
Complex
r(Ni–Se)
r(C–Se)
r(C=C)
Ni(1')22–
2.231
1.757
1.351
Ni(1)22–
2.354
1.908
1.346
Ni(2')22–
2.203
1.742
1.380
Ni(2)22–
2.330
1.893
1.374
Ni(3')22–
2.200
1.745
1.367
Ni(3)22–
2.323
1.899
1.361
Ni(4')22–
2.218
1.746
1.418
Ni(4)22–
2.345
1.903
1.410
Ni(5')22–
2.202
1.730
1.424
Ni(5)22–
2.329
1.884
1.418
Ni(6')22–
2.211
1.733
1.442
Ni(6)22–
2.337
1.889
1.436
Table S6. Selected average bond lengths for the neutral bisdithiolene- and
bisdiselenolene-Pd complexes
Complex
r(Pd–S) r(C–S)
r(C=C)
Complex
r(Pd–Se)
r(C–Se)
r(C=C)
Pd(1')20
2.289
1.705
1.386
Pd(1)20
2.409
1.856
1.377
Pd(2')20
2.289
1.702
1.399
Pd(2)20
2.410
1.854
1.390
Pd(3')20
2.279
1.699
1.385
Pd(3)20
2.399
1.854
1.375
Pd(4')20
2.291
1.718
1.421
Pd(4)20
2.412
1.872
1.415
Pd(5')20
2.291
1.713
1.423
Pd(5)20
2.411
1.867
1.416
Pd(6')20
2.297
1.713
1.428
Pd(6)20
2.418
1.870
1.422
5
Table S7. Selected average bond lengths for the monoanionic bisdithiolene- and
bisdiselenolene-Pd complexes
Complex
r(Pd–S)
r(C–S)
r(C=C) Complex
r(Pd–Se)
r(C–Se)
r(C=C)
Pd(1')21–
2.318
1.733
1.364
Pd(1)21–
2.439
1.885
1.357
Pd(2')21–
2.310
1.725
1.383
Pd(2)21–
2.432
1.876
1.377
Pd(3')21–
2.303
1.726
1.371
Pd(3)21–
2.422
1.880
1.364
Pd(4')21–
2.317
1.739
1.414
Pd(4)21–
2.438
1.893
1.408
Pd(5')21–
2.312
1.729
1.418
Pd(5)21–
2.433
1.883
1.413
Pd(6')21–
2.319
1.729
1.432
Pd(6)21–
2.441
1.885
1.425
Table S8. Selected average bond lengths for the dianionic bisdithiolene- and
bisdiselenolene-Pd complexes
Complex r(Pd–S)
r(C–S)
r(C=C)
Complex
r(Pd–Se)
r(C–Se)
r(C=C)
Pd(1')22–
2.364
1.760
1.351
Pd(1)22–
2.485
1.911
1.346
Pd(2')22–
2.344
1.745
1.378
Pd(2)22–
2.466
1.896
1.373
Pd(3')22–
2.339
1.750
1.367
Pd(3)22–
2.458
1.904
1.361
Pd(4')22–
2.354
1.751
1.418
Pd(4)22–
2.477
1.907
1.410
Pd(5')22–
2.340
1.734
1.425
Pd(5)22–
2.462
1.889
1.418
Pd(6')22–
2.349
1.736
1.443
Pd(6)22–
2.472
1.893
1.436
Table S9. Selected average bond lengths for the neutral bisdithiolene- and
bisdiselenolene-Pt complexes
Complex r(Pt–S)
r(C–S)
r(C=C) Complex
r(Pt–Se)
r(C–Se)
r(C=C)
Pt(1')20
2.278
1.706
1.381
Pt(1)20
2.404
1.857
1.373
Pt(2')20
2.277
1.704
1.396
Pt(2)20
2.404
1.855
1.387
Pt(3')20
2.269
1.701
1.381
Pt(3)20
2.395
1.855
1.372
6
Pt(4')20
2.281
1.719
1.417
Pt(4)20
2.407
1.873
1.411
Pt(5')20
2.280
1.715
1.419
Pt(5)20
2.406
1.868
1.413
Pt(6')20
2.286
1.715
1.424
Pt(6)20
2.412
1.871
1.418
Table S10. Selected average bond lengths for the monoanionic bisdithiolene- and
bisdiselenolene-Pt complexes
Complex r(Pt–S)
r(C–S)
r(C=C) Complex
r(Pt–Se)
r(C–Se)
r(C=C)
Pt(1')21–
2.306
1.734
1.362
Pt(1)21–
2.432
1.885
1.355
Pt(2')21–
2.298
1.726
1.382
Pt(2)21–
2.425
1.877
1.376
Pt(3')21–
2.292
1.727
1.370
Pt(3)21–
2.417
1.881
1.363
Pt(4')21–
2.306
1.739
1.412
Pt(4)21–
2.432
1.893
1.406
Pt(5')21–
2.301
1.729
1.417
Pt(5)21–
2.427
1.883
1.411
Pt(6')21–
2.308
1.730
1.429
Pt(6)21–
2.435
1.885
1.424
Table S11. Selected average bond lengths for the dianionic bisdithiolene- and
bisdiselenolene-Pt complexes
Complex r(Pt–S)
r(C–S)
r(C=C) Complex
r(Pt–Se)
r(C–Se)
r(C=C)
Pt(1')22–
2.346
1.759
1.352
Pt(1)22–
2.472
1.910
1.346
Pt(2')22–
2.329
1.744
1.380
Pt(2)22–
2.455
1.896
1.374
Pt(3')22–
2.325
1.749
1.368
Pt(3)22–
2.449
1.903
1.362
Pt(4')22–
2.338
1.750
1.418
Pt(4)22–
2.466
1.906
1.410
Pt(5')22–
2.325
1.733
1.425
Pt(5)22–
2.452
1.888
1.418
Pt(6')22–
2.334
1.735
1.443
Pt(6)22–
2.462
1.891
1.436
Table S12. The HOMO-LUMO gap energies for [M(L)2]z and [M(L’)2]z (z = 0, 1–; M =
Ni, Pd, Pt).
EHOMO-LUMO
(eV)
EHOMO-LUMO
(eV)
EHOMO-LUMO
(eV)
7
Pt(1')20
Pt(2')20
Pt(3')20
Pt(4')20
Pt(5')20
Pt(6')20
2.090
2.112
2.285
2.026
2.019
1.979
Ni(1)20
Ni(2)20
Ni(3)20
Ni(4)20
Ni(5)20
Ni(6)20
EHOMO-LUMO
(eV)
2.078
2.144
2.294
2.020
2.056
2.063
Ni(1')21–
Ni(2')21–
Ni(3')21–
Ni(4')21–
Ni(5')21–
Ni(6')21–
EHOMOβ-LUMOβ
(eV)
2.187
2.353
2.498
2.282
2.358
2.286
Ni(1)21–
Ni(2)21–
Ni(3)21–
Ni(4)21–
Ni(5)21–
Ni(6)21–
EHOMOβ-LUMOβ
(eV)
2.208
2.410
2.546
2.173
2.233
2.297
Pd(1')20
Pd(2')20
Pd(3')20
Pd(4')20
Pd(5')20
Pd(6')20
1.859
1.901
2.048
1.836
1.840
1.797
Pd(1)20
Pd(2)20
Pd(3)20
Pd(4)20
Pd(5)20
Pd(6)20
EHOMO-LUMO
(eV)
1.835
1.901
2.026
1.852
1.873
1.841
Pd(1')21–
Pd(2')21–
Pd(3')21–
Pd(4')21–
Pd(5')21–
Pd(6')21–
EHOMOβ-LUMOβ
(eV)
1.905
2.032
2.157
1.951
1.989
1.911
Pd(1)21–
Pd(2)21–
Pd(3)21–
Pd(4)21–
Pd(5)21–
Pd(6)21–
EHOMOβ-LUMOβ
(eV)
1.880
2.017
2.121
1.880
1.910
1.939
Pt(1')20
Pt(2')20
Pt(3')20
Pt(4')20
Pt(5')20
Pt(6')20
2.156
2.248
2.413
2.132
2.156
2.138
Pt(1)20
Pt(2)20
Pt(3)20
Pt(4)20
Pt(5)20
Pt(6)20
EHOMO-LUMO
(eV)
2.088
2.198
2.334
1.877
1.903
1.978
Pt(1')21–
Pt(2')21–
Pt(3')21–
Pt(4')21–
Pt(5')21–
Pt(6')21–
EHOMOβ-LUMOβ
(eV)
2.113
2.278
2.413
2.132
2.184
2.151
Pt(1)21–
Pt(2)21–
Pt(3)21–
Pt(4)21–
Pt(5)21–
Pt(6)21–
EHOMOβ-LUMOβ
(eV)
2.089
2.267
2.384
1.987
2.033
2.065
8
Table S13. The T1 diagnostic values obtained with the CCSD method. The LANL2DZ(f)
basis set was used for the Ni, Pd and Pt atoms. For all other atoms the 6-311G(d,p) basis
set with ECPs in the LANL2DZ basis set to describe the core electrons of the S and Se
atoms was used.
Complex
T1
Complex
T1
Complex
T1
[Ni(S2C2CH3)2]0
0.05
[Pd(S2C2CH3)2]0
0.02
[Pt(S2C2CH3)2]0
0.02
[Ni(Se2C2CH3)2]0
0.05
[Pd(S2C2CH3)2]0
0.02
[Pt(S2C2CH3)2]0
0.02
[Ni(S2C2CH3)2]2–
0.04
[Pd(S2C2CH3)2]2–
0.02
[Pt(S2C2CH3)2]2–
0.02
[Ni(Se2C2CH3)2]2–
0.04
[Pd(S2C2CH3)2]2–
0.02
[Pt(S2C2CH3)2]2–
0.02
[Ni(S2C2(CN)2)2]0
0.05
[Pd(S2C2(CN)2)2]0
0.02
[Pt(S2C2(CN)2)2]0
0.02
[Ni(Se2C2(CN)2)2]0
0.05
[Pd(S2C2(CN)2)2]0
0.02
[Pt(S2C2(CN)2)2]0
0.02
[Ni(S2C2(CN)2)2]2–
0.04
[Pd(S2C2(CN)2)2]2–
0.02
[Pt(S2C2(CN)2)2]2–
0.02
[Ni(Se2C2(CN)2)2]2–
0.04
[Pd(S2C2(CN)2)2]2–
0.02
[Pt(S2C2(CN)2)2]2–
0.02
9
Table S14. Calculated S2 for [M(L)2]0, [M(L)2]1–, [M(L)2]2–, [M(L')2]0, [M(L')2]1– and
[M(L')2]2– (M = Ni, Pd and Pt) at the IEFPCM-M06/BS1//M06-L/BS1 level of theory.
Ni
Pd
Pt
Ni
Pd
0
0
[M(1)2]
0.00
0.00
0.00
[M(1')2]
0.00
0.00
0
0
[M(2)2]
0.00
0.00
0.00
[M(2')2]
0.00
0.00
0
0
[M(3)2]
0.00
0.00
0.00
[M(3')2]
0.00
0.00
0
0
[M(4)2]
0.00
0.00
0.00
[M(4')2]
0.00
0.00
0
0
[M(5)2]
0.00
0.00
0.00
[M(5')2]
0.00
0.00
0
0
[M(6)2]
0.00
0.00
0.00
[M(6')2]
0.00
0.00
Pt
0.00
0.00
0.00
0.00
0.00
0.00
[M(1)2]1–
[M(2)2]1–
[M(3)2]1–
[M(4)2]1–
[M(5)2]1–
[M(6)2]1–
0.76
0.77
0.77
0.76
0.77
0.77
0.76
0.76
0.76
0.76
0.76
0.76
0.76
0.76
0.76
0.76
0.76
0.76
[M(1')2]1–
[M(2')2]1–
[M(3')2]1–
[M(4')2]1–
[M(5')2]1–
[M(6')2]1–
0.76
0.76
0.76
0.76
0.76
0.76
0.75
0.76
0.76
0.75
0.76
0.76
0.75
0.76
0.76
0.76
0.76
0.76
[M(1)2]2–
[M(2)2]2–
[M(3)2]2–
[M(4)2]2–
[M(5)2]2–
[M(6)2]2–
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
[M(1')2]2–
[M(2')2]2–
[M(3')2]2–
[M(4')2]2–
[M(5')2]2–
[M(6')2]2–
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
10