Butadienyl Diiron Complexes : Nonplanar Metalla-Aromatics Involving σ-Type Orbital Overlap
© 2020 Wiley-VCH GmbH..
A new class of nonplanar metalla-aromatics, diiron complexes bridged by a 1,3-butadienyl dianionic ligand, were synthesized in high yields from dilithio reagents and two equivalents of FeBr2 . The complexes consist of two antiferromagnetically coupled high-spin FeII centers, as revealed by magnetometry, Mössbauer spectroscopy, and DFT calculations. Furthermore, experimental (X-ray structural analysis) and theoretical analyses (NICS, ICSS, AICD, MOs) suggest that the complexes are aromatic. Remarkably, this nonplanar metalla-aromaticity is achieved by an uncommon σ-type overlap between the ligand p and metal d orbitals, in sharp contrast to the intensively studied planar aromatic systems featuring delocalized π-type bonding. Specifically, the σ-type interaction between the two Fe 3dxz orbitals and the butadienyl π orbital results in the formation of a six-electron conjugated system and hence enables the aromatic character.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:59 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 59(2020), 43 vom: 19. Okt., Seite 19048-19053 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Yu, Chao [VerfasserIn] |
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| Links: |
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| Themen: |
σ-type overlap |
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| Anmerkungen: |
Date Revised 08.12.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202008986 |
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| funding: |
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NLM312626061 |
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a © 2020 Wiley-VCH GmbH. | ||
| 520 | |a A new class of nonplanar metalla-aromatics, diiron complexes bridged by a 1,3-butadienyl dianionic ligand, were synthesized in high yields from dilithio reagents and two equivalents of FeBr2 . The complexes consist of two antiferromagnetically coupled high-spin FeII centers, as revealed by magnetometry, Mössbauer spectroscopy, and DFT calculations. Furthermore, experimental (X-ray structural analysis) and theoretical analyses (NICS, ICSS, AICD, MOs) suggest that the complexes are aromatic. Remarkably, this nonplanar metalla-aromaticity is achieved by an uncommon σ-type overlap between the ligand p and metal d orbitals, in sharp contrast to the intensively studied planar aromatic systems featuring delocalized π-type bonding. Specifically, the σ-type interaction between the two Fe 3dxz orbitals and the butadienyl π orbital results in the formation of a six-electron conjugated system and hence enables the aromatic character | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a butadienyl dianion | |
| 650 | 4 | |a diiron complexes | |
| 650 | 4 | |a metalla-aromatics | |
| 650 | 4 | |a nonplanar aromaticity | |
| 650 | 4 | |a σ-type overlap | |
| 700 | 1 | |a Zhong, Mingdong |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Yongliang |e verfasserin |4 aut | |
| 700 | 1 | |a Wei, Junnian |e verfasserin |4 aut | |
| 700 | 1 | |a Ma, Wangyang |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Wen-Xiong |e verfasserin |4 aut | |
| 700 | 1 | |a Ye, Shengfa |e verfasserin |4 aut | |
| 700 | 1 | |a Xi, Zhenfeng |e verfasserin |4 aut | |
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