Результаты исследований: Научные публикации в периодических изданиях › Обзорная статья › Рецензирование
Iron bispentazole Fe(η5-N5)2, a theoretically predicted high-energy compound : Structure, bonding analysis, metal-ligand bond strength and a comparison with the isoelectronic ferrocene. / Lein, Matthias; Frunzke, Jan; Timoshkin, Alexey; Frenking, Gernot.
в: Chemistry - A European Journal, Том 7, № 19, 01.10.2001, стр. 4155-4163.Результаты исследований: Научные публикации в периодических изданиях › Обзорная статья › Рецензирование
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TY - JOUR
T1 - Iron bispentazole Fe(η5-N5)2, a theoretically predicted high-energy compound
T2 - Structure, bonding analysis, metal-ligand bond strength and a comparison with the isoelectronic ferrocene
AU - Lein, Matthias
AU - Frunzke, Jan
AU - Timoshkin, Alexey
AU - Frenking, Gernot
PY - 2001/10/1
Y1 - 2001/10/1
N2 - 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.
AB - 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.
KW - Bonding analysis
KW - Density functional calculations
KW - Donor-acceptor systems
KW - Ferrocene
KW - Pentazole complexes
UR - http://www.scopus.com/inward/record.url?scp=0035476626&partnerID=8YFLogxK
U2 - 10.1002/1521-3765(20011001)7:19<4155::AID-CHEM4155>3.0.CO;2-M
DO - 10.1002/1521-3765(20011001)7:19<4155::AID-CHEM4155>3.0.CO;2-M
M3 - Review article
C2 - 11686594
AN - SCOPUS:0035476626
VL - 7
SP - 4155
EP - 4163
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 19
ER -
ID: 17371202