Результаты исследований: Научные публикации в периодических изданиях › Обзорная статья › Рецензирование
Quantum-chemical calculations with gradient-corrected (B3LYP) density functional theory have been carried out for iron bispentazole and ferrocene. The calculations predict that Fe(η5-N5)2 is a strongly bonded complex which has D5d symmetry. The theoretically predicted total bond energy that yields Fe in the 5D ground state and two pentazole ligands is Do= 109.0 kcal mol-1, which is only 29 kcal mol-1 less than the calculated bond energy of ferrocene (Do= 138.0 kcal mol-1; experimental: 158± 2 kcal mol-1). The compound Fe(η5-N5)2 is 260.5 kcal mol-1 higher in energy than the experimentally known isomer Fe(N2)5, but the bond energy of the latter (Do=33.7 kcal mol-1) is much less. The energy decomposition analyses of Fe(η5-N5)2 and ferrocene show that the two compounds have similar bonding situations. The metal-ligand bonds are roughly half ionic and half covalent. The covalent bonding comes mainly from (e1g) η5-N5 - → Fe2+ π-donation. The previously suggested MO correlation diagram for ferrocene is nicely recovered by the Kohn-Sham orbitals. The calculated vibrational frequencies and IR intensities are reported.
Язык оригинала | английский |
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Страницы (с-по) | 4155-4163 |
Число страниц | 9 |
Журнал | Chemistry - A European Journal |
Том | 7 |
Номер выпуска | 19 |
DOI | |
Состояние | Опубликовано - 1 окт 2001 |
Опубликовано для внешнего пользования | Да |
ID: 17371202