Table 3 Calculated free energies (kcal/mol) for the addition of one and two molecules of benzaldehyde to [X]2– and selected bond lengths (Å)
From: Transforming carbon dioxide into a methanol surrogate using modular transition metal-free Zintl ions
| ||||
|---|---|---|---|---|
E–Pn (Å) | Pn–C (Å) | E–O (Å) | ΔG (kcal/mol) | |
[1]2– | 2.09 | |||
[1]2– + C6H5CHO→[1]2–•C6H5CHO | 2.11 | 1.95 | 1.48 | –11.5 |
[1]2–•C6H5CHO + C6H5CHO→[1]2–• 2C6H5CHO | 1.95 | 1.51 | +1.1 | |
[(Me2Al)P7]2– | 2.45 | |||
[(Me2Al)P7]2– + C6H5CHO→[(Me2Al)P7]2–•C6H5CHO | 2.44 | 1.96 | 1.79 | –13.6 |
[(Me2Al)P7]2–•C6H5CHO + C6H5CHO→[(Me2Al)P7]2–•2C6H5CHO | 1.96 | 1.79 | –1.8 | |
[(Me2Al)As7]2– | 2.55 | |||
[(Me2Al)As7]2– + C6H5CHO→[(Me2Al)As7]2–•C6H5CHO | 2.54 | 2.10 | 1.79 | –12.0 |
[(Me2Al)As7]2–•C6H5CHO + C6H5CHO→[(Me2Al)As7]2–•2C6H5CHO | 2.11 | 1.79 | –2.7 | |
[4]2– | 2.63 | |||
[4]2– + C6H5CHO→[4]2–•C6H5CHO | 2.57 | 1.98 | 2.13 | +4.2 |
[4]2–•C6H5CHO + C6H5CHO→[4]2–•2C6H5CHO | 1.95 | 2.13 | +13.8 | |
[(Me2Ga)P7]2– | 2.47 | |||
[(Me2Ga)P7]2– + C6H5CHO→[(Me2Ga)P7]2–•C6H5CHO | 2.43 | 1.97 | 1.91 | −2.0 |
[(Me2Ga)P7]2–•C6H5CHO + C6H5CHO→[(Me2Ga)P7]2–•2C6H5CHO | 1.97 | 1.90 | +10.3 | |
