Table 6. Electronic and Gibbs Free Energies (in the Gas Phase and in Water) for the DO2A2S Complexes of Cu2+ and Cu+a.
| gas phase |
water |
|||||
|---|---|---|---|---|---|---|
| M | coordination | formb | ΔE | ΔG | ΔE | ΔG |
| Cu2+ | [4N,2O] | –698.8 | –684.7 | –220.8 | –206.7 | |
| [4N,2O] | H+ | –563.3 | –548.3 | –202.6 | –187.6 | |
| [4N,O] | H+ | –565.7 | –550.1 | –210.5 | –194.9 | |
| [4N,O,S] | H+ | –563.8 | –546.4 | –201.0 | –183.7 | |
| [4N,S] | H+ | –554.6 | –539.4 | –198.8 | –183.6 | |
| [4N,2S] | H+ | –545.5 | –528.2 | –186.7 | –169.4 | |
| Cu+ | [4N,2O] | –260.6 | –260.6 | –66.3 | –57.2 | |
| [4N,O] | –257.7 | –257.7 | –75.5 | –66.0 | ||
| [4N,O,S] | –253.1 | –253.1 | –71.4 | –61.0 | ||
| [4N,S] | –248.1 | –248.1 | –77.8 | –67.8 | ||
| [4N,2S] | –243.7 | –243.7 | –69.1 | –56.2 | ||
| [4N,2O] | H+ | –193.4 | –193.4 | –63.1 | –50.5 | |
| [4N,O] | H+ | –203.1 | –203.1 | –73.1 | –59.8 | |
| [4N,O,S] | H+ | –199.6 | –199.6 | –68.7 | –54.1 | |
| [4N,S] | H+ | –188.1 | –188.1 | –96.9 | –82.4 | |
| [4N,2S] | H+ | –184.2 | –184.2 | –65.2 | –48.7 | |
a
All of the energies are in kilocalories per mole. Level of theory: (COSMO-)ZORA-OPBE/TZ2P//ZORA-OPBE/TZP.
b
The two carboxylates were considered to be either deprotonated (−) or monoprotonated (H+).