A Computational Study Into the Redox Chemistry of Mo- and W-Trisdiselenolene Complexes

A Computational Study into the Redox Chemistry of Mo- and W-trisdiselenolene complexes.

Eric A. C. Bushnell*1, Matt R. Adams2 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

5 Tables,7 Pages in total.

Table S1. Selected average bond lengths of the neutral mono-anionic and di-anionic Mo-trisdithiolene- and trisdiselenolene complexes.

(Mo-S)avg / (C-S)avg / (C-C)avg
[Mo(1')3]0 / 2.403 / 1.725 / 1.378
[Mo(2')3]0 / 2.394 / 1.737 / 1.393
[Mo(3')3]0 / 2.397 / 1.738 / 1.405
[Mo(4')3]0 / 2.388 / 1.734 / 1.391
(Mo-Se)avg / (C-Se)avg / (C-C)avg
[Mo(1)3]0 / 2.529 / 1.873 / 1.369
[Mo(2)3]0 / 2.518 / 1.887 / 1.384
[Mo(3)3]0 / 2.512 / 1.89 / 1.397
[Mo(4)3]0 / 2.512 / 1.888 / 1.382
(Mo-X)avg / (C-S)avg / (C-C)avg
[Mo(1')3]1– / 2.422 / 1.741 / 1.369
[Mo(2')3]1– / 2.411 / 1.758 / 1.379
[Mo(3')3]1– / 2.408 / 1.75 / 1.396
[Mo(4')3]1– / 2.402 / 1.748 / 1.383
(Mo-Se)avg / (C-Se)avg / (C-C)avg
[Mo(1)3]1– / 2.547 / 1.889 / 1.362
[Mo(2)3]1– / 2.536 / 1.903 / 1.373
[Mo(3)3]1– / 2.531 / 1.901 / 1.390
[Mo(4)3]1– / 2.523 / 1.902 / 1.376
(Mo-X)avg / (C-S)avg / (C-C)avg
[Mo(1')3]2– / 2.439 / 1.758 / 1.366
[Mo(2')3]2– / 2.427 / 1.775 / 1.372
[Mo(3')3]2– / 2.413 / 1.761 / 1.396
[Mo(4')3]2– / 2.409 / 1.762 / 1.382
(Mo-Se)avg / (C-Se)avg / (C-C)avg
[Mo(1)3]2– / 2.561 / 1.907 / 1.360
[Mo(2)3]2– / 2.550 / 1.929 / 1.366
[Mo(3)3]2– / 2.535 / 1.913 / 1.391
[Mo(4)3]2– / 2.530 / 1.917 / 1.377

Table S2. Selected average bond lengths of the neutral mono-anionic and di-anionic W-trisdithiolene- and trisdiselenolene complexes.

(W-S)avg / (C-S)avg / (C-C)avg
[W(1')3]0 / 2.402 / 1.731 / 1.374
[W(2')3]0 / 2.393 / 1.745 / 1.388
[W(3')3]0 / 2.395 / 1.745 / 1.401
[W(4')3]0 / 2.388 / 1.740 / 1.386
(W-Se)avg / (C-Se)avg / (C-C)avg
[W(1)3]0 / 2.531 / 1.878 / 1.367
[W(2)3]0 / 2.521 / 1.893 / 1.381
[W(3)3]0 / 2.523 / 1.895 / 1.394
[W(4)3]0 / 2.515 / 1.894 / 1.379
(W-S)avg / (C-S)avg / (C-C)avg
[W(1')3]1– / 2.421 / 1.747 / 1.366
[W(2')3]1– / 2.409 / 1.765 / 1.375
[W(3')3]1– / 2.407 / 1.755 / 1.393
[W(4')3]1– / 2.401 / 1.753 / 1.379
(W-Se)avg / (C-Se)avg / (C-C)avg
[W(1)3]1– / 2.549 / 1.893 / 1.360
[W(2)3]1– / 2.537 / 1.912 / 1.370
[W(3)3]1– / 2.533 / 1.906 / 1.388
[W(4)3]1– / 2.526 / 1.907 / 1.374
(W-S)avg / (C-S)avg / (C-C)avg
[W(1')3]2– / 2.434 / 1.764 / 1.364
[W(2')3]2– / 2.422 / 1.781 / 1.368
[W(3')3]2– / 2.408 / 1.767 / 1.394
[W(4')3]2– / 2.406 / 1.768 / 1.380
(W-Se)avg / (C-Se)avg / (C-C)avg
[W(1)3]2– / 2.559 / 1.912 / 1.358
[W(2)3]2– / 2.549 / 1.934 / 1.363
[W(3)3]2– / 2.533 / 1.919 / 1.389
[W(4)3]2– / 2.530 / 1.923 / 1.374

Table S3. The calculated average values of the fold angle (θ) and twist angle (Φ) for the Mo-tris(dithiolene) and tris(diselenolene) complexes investigate herein.

θ avg / Φavg
[Mo(1')3]0 / 17.7 / 0.0
[Mo(2')3]0 / 17.0 / 0.0
[Mo(3')3]0 / 18.9 / 0.0
[Mo(4')3]0 / 19.0 / 0.0
θ avg / Φavg
[Mo(1)3]0 / 17.7 / 0.0
[Mo(2)3]0 / 17.2 / 0.0
[Mo(3)3]0 / 19.5 / 0.0
[Mo(4)3]0 / 19.6 / 0.1
θ avg / Φavg
[Mo(1')3]1– / 11.5 / 0.0
[Mo(2')3]1– / 12.1 / 0.1
[Mo(3')3]1– / 11.9 / 0.0
[Mo(4')3]1– / 12.2 / 1.2
θ avg / Φavg
[Mo(1)3]1– / 11.9 / 0.0
[Mo(2)3]1– / 10.3 / 0.1
[Mo(3)3]1– / 11.7 / 0.0
[Mo(4)3]1– / 12.3 / 1.5
θ avg / Φavg
[Mo(1')3]2– / 0.0 / 22.4
[Mo(2')3]2– / 0.1 / 15.9
[Mo(3')3]2– / 0.0 / 26.1
[Mo(4')3]2– / 0.4 / 22.8
θ avg / Φavg
[Mo(1)3]2– / 0.0 / 24.7
[Mo(2)3]2– / 0.1 / 20.0
[Mo(3)3]2– / 0.0 / 26.9
[Mo(4)3]2– / 0.4 / 24.1

Table S4. The calculated average values of the fold angle (θ) and twist angle (Φ) for the W-tris(dithiolene) and tris(diselenolene) complexes investigate herein.

θ avg / Φavg
[W(1')3]0 / 20.3 / 0.0
[W(2')3]0 / 19.8 / 0.0
[W(3')3]0 / 21.4 / 0.0
[W(4')3]0 / 21.4 / 0.5
θ avg / Φavg
[W(1)3]0 / 20.3 / 0.0
[W(2)3]0 / 19.9 / 0.0
[W(3)3]0 / 22.0 / 0.0
[W(4)3]0 / 22.0 / 0.0
θ avg / Φavg
[W(1')3]1– / 13.1 / 0.0
[W(2')3]1– / 13.5 / 0.0
[W(3')3]1– / 13.4 / 0.0
[W(4')3]1– / 13.5 / 0.5
θ avg / Φavg
[W(1)3]1– / 13.4 / 0.0
[W(2)3]1– / 13.7 / 0.0
[W(3)3]1– / 13.3 / 0.1
[W(4)3]1– / 13.6 / 1.8
θ avg / Φavg
[W(1')3]2– / 0.0 / 20.8
[W(2')3]2– / 0.4 / 12.9
[W(3')3]2– / 0.0 / 26.1
[W(4')3]2– / 0.3 / 22.0
θ avg / Φavg
[W(1)3]2– / 0.1 / 23.3
[W(2)3]2– / 0.4 / 17.9
[W(3)3]2– / 0.1 / 26.9
[W(4)3]2– / 0.4 / 23.6

Table S5. The HOMO-LUMO energy gapsfor [M(L)3]z and [M(L’)3]z (z = 0, 1–).

Complex / EHOMO-LUMOAvg (eV) / Complex / EHOMO-LUMOAvg (eV)
[Mo(1)2]0 / 2.63 / [Mo(1')2]0 / 2.77
[Mo(2)2]0 / 2.57 / [Mo(2')2]0 / 2.72
[Mo(3)2]0 / 2.69 / [Mo(3')2]0 / 2.73
[Mo(4)2]0 / 2.78 / [Mo(4')2]0 / 2.86
Complex / EHOMOβ-SOMOβAvg (eV) / Complex / EHOMOβ-SOMOβAvg (eV)
[Mo(1)2]1– / 2.30 / [Mo(1')2]1– / 2.30
[Mo(2)2]1– / 2.27 / [Mo(2')2]1– / 2.31
[Mo(3)2]1– / 2.32 / [Mo(3')2]1– / 2.27
[Mo(4)2]1– / 2.39 / [Mo(4')2]1– / 2.36
Complex / EHOMO-LUMOAvg (eV) / Complex / EHOMO-LUMOAvg (eV)
[W(1)2]0 / 2.75 / [W(1')2]0 / 2.90
[W(2)2]0 / 2.68 / [W(2')2]0 / 2.83
[W(3)2]0 / 2.81 / [W(3')2]0 / 2.85
[W(4)2]0 / 2.90 / [W(4')2]0 / 2.99
Complex / EHOMOβ-SOMOβAvg (eV) / Complex / EHOMOβ-SOMOβAvg (eV)
[W(1)2]1– / 2.30 / [W(1')2]1– / 2.35
[W(2)2]1– / 2.29 / [W(2')2]1– / 2.34
[W(3)2]1– / 2.31 / [W(3')2]1– / 2.31
[W(4)2]1– / 2.38 / [W(4')2]1– / 2.41

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