Table 3.
DFT calculated data from this data article, as well as experimental electrochemical data (E vs Fc/Fc+) obtained from literature [4,5], of the [Ru(β-diketonato)3] compounds 1 – 14. Where β-diketonato ligand = (RCOCHCORꞌ)— with the R and Rꞌ substituents as shown in Fig. 1. DFT data was computed using two different hybrid functionals OPBE0 and B3LYP.
| R | R' | E (RuIII/II) a | E (RuIII/IV) a | OPBE0/STO-TZ2P |
B3LYP/STO-TZ2P |
B3LYP/STO-6-311G(d,p)/Lanl2dz |
|||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| EHOMO (eV) | ELUMO (eV) | χcalc (eV) c | EHOMO (eV) | ELUMO (eV) | χcalc (eV) c | EHOMO (eV) | ELUMO (eV) | χcalc (eV) c | |||||
| 1 | CF3 | CF3 | 0.34 | -7.183 | -4.200 | 5.692 | -6.938 | -4.558 | 5.748 | -7.507 | -3.272 | 5.389 | |
| 2 | CF3 | C4H3O | -0.34 | 1.20 | -6.404 | -3.408 | 4.906 | -6.103 | -3.725 | 4.914 | -6.607 | -2.768 | 4.688 |
| 3 | CF3 | C4H3S | -0.35 | 1.19 | -6.393 | -3.410 | 4.901 | -6.074 | -3.707 | 4.890 | -6.635 | -2.822 | 4.729 |
| 4 | CF3 | Ph | -0.35 | 1.26 | -6.528 | -3.482 | 5.005 | -6.168 | -3.765 | 4.967 | -6.777 | -2.758 | 4.767 |
| 5 | CF3 | CH3 | -0.47 | 1.29 | -6.519 | -3.413 | 4.966 | -6.211 | -3.792 | 5.001 | -6.815 | -2.414 | 4.615 |
| 6 | CF3 | C(CH3)3 | -0.55 | 1.30 | -6.420 | -3.341 | 4.881 | -6.165 | -3.732 | 4.949 | -6.745 | -2.353 | 4.549 |
| 7 | Ph | Ph | -0.90 | 0.66 | -5.987 | -2.978 | 4.483 | -5.620 | -3.211 | 4.415 | -6.229 | -2.405 | 4.317 |
| 8 | CH3 | Ph | -1.04 | 0.64 | -5.922 | -2.863 | 4.393 | -5.595 | -3.132 | 4.364 | -6.216 | -2.137 | 4.177 |
| 9 | CH3 | CH3 | -1.16 | 0.61 | -5.863 | -2.719 | 4.291 | -5.215 | -2.785 | 4.000 | -6.166 | -1.634 | 3.900 |
| 10 | C(CH3)3 | C(CH3)3 | -1.46 | 0.44 | -5.467 | -2.403 | 3.935 | -5.215 | -2.785 | 4.000 | -6.021 | -1.474 | 3.748 |
| 11 | Et | Et | -1.308 | 0.549 | -5.722 | -2.588 | 4.155 | -5.435 | -2.962 | 4.199 | -6.151 | -1.648 | 3.900 |
| 12 | Pr | Pr | -1.324 | 0.547 | -5.703 | -2.577 | 4.140 | -5.415 | -2.938 | 4.177 | -6.136 | -1.633 | 3.884 |
| 13 | Bu | Bu | -1.330 | 0.535 | -5.681 | -2.565 | 4.123 | -5.415 | -2.946 | 4.180 | -6.130 | -1.619 | 3.874 |
| 14 | iPr | iPr | -1.392 | 0.509 | -5.523 | -2.470 | 3.996 | -5.289 | -2.836 | 4.062 | -6.123 | -1.591 | 3.857 |
a
Experimental values for E vs Fc/Fc+ from references [4,5]. In order to convert to potential vs Fc/Fc+ for comparative reasons, the following values have been used:
E°' (Fc/Fc+) = 0.66(5) V vs NHE in solvent [n(Bu4)N][PF6]/CH3CN [9]; Saturated calomel (SCE) = 0.2444 V vs NHE; Ag/Ag+ = 0.400 V vs SCE [10].
bχ = Electronegativity