Details
| Original language | English |
|---|---|
| Pages (from-to) | 378-387 |
| Number of pages | 10 |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 2017 |
| Issue number | 2 |
| Early online date | 10 Aug 2016 |
| Publication status | Published - 12 Jan 2017 |
Abstract
1,2-Disubstituted ferrocenes, in particular 1,2-dihaloferrocenes, are important starting materials. Herein, we describe significantly improved high-yielding syntheses of 1,2-disubstituted ferrocenes such as 1,2-dibromo- and 1,2-diiodoferrocene as well as 1-bromo-2-iodoferrocene, and 1-bromo-2-fluoroferrocene. DFT calculations show that 1,2-dihaloferrocenes do not differ much in their highest occupied molecular orbital (HOMO) energies; however, their lowest unoccupied molecular orbital (LUMO) energies – and thus the HOMO/LUMO gaps – correlate with the sum of the halogen electronegativities. In addition, a synthesis of the rather sensitive 2-aminoferrocenecarboxylic acid, the ferrocene analogue of anthranilic acid, is presented, which starts from ferrocene-1,2-dicarboxylic acid. However, 2-aminoferrocenecarboxylic acid rapidly decomposed and thus could not be properly characterized. Ferrocene-1,2-dicarboxylic anhydride serves as the starting material for preliminary photochemical decarbonylation/decarboxylation experiments resulting in 1,2-dideuterioferrocene when carried out in [D8]toluene.
Keywords
- Ferrocene, Halogenation, Iron, Lithiation, Sandwich complexes
ASJC Scopus subject areas
- Chemistry(all)
- Inorganic Chemistry
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In: European Journal of Inorganic Chemistry, Vol. 2017, No. 2, 12.01.2017, p. 378-387.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Improved Syntheses of 1,2-Disubstituted Ferrocenes
AU - Werner, Georg
AU - Butenschön, Holger
N1 - Funding Information: This work was generously supported by the Deutsche Forschungsgemeinschaft (BU 814/16-1). We thank Innospec Deutschland GmbH for a donation of ferrocene.
PY - 2017/1/12
Y1 - 2017/1/12
N2 - 1,2-Disubstituted ferrocenes, in particular 1,2-dihaloferrocenes, are important starting materials. Herein, we describe significantly improved high-yielding syntheses of 1,2-disubstituted ferrocenes such as 1,2-dibromo- and 1,2-diiodoferrocene as well as 1-bromo-2-iodoferrocene, and 1-bromo-2-fluoroferrocene. DFT calculations show that 1,2-dihaloferrocenes do not differ much in their highest occupied molecular orbital (HOMO) energies; however, their lowest unoccupied molecular orbital (LUMO) energies – and thus the HOMO/LUMO gaps – correlate with the sum of the halogen electronegativities. In addition, a synthesis of the rather sensitive 2-aminoferrocenecarboxylic acid, the ferrocene analogue of anthranilic acid, is presented, which starts from ferrocene-1,2-dicarboxylic acid. However, 2-aminoferrocenecarboxylic acid rapidly decomposed and thus could not be properly characterized. Ferrocene-1,2-dicarboxylic anhydride serves as the starting material for preliminary photochemical decarbonylation/decarboxylation experiments resulting in 1,2-dideuterioferrocene when carried out in [D8]toluene.
AB - 1,2-Disubstituted ferrocenes, in particular 1,2-dihaloferrocenes, are important starting materials. Herein, we describe significantly improved high-yielding syntheses of 1,2-disubstituted ferrocenes such as 1,2-dibromo- and 1,2-diiodoferrocene as well as 1-bromo-2-iodoferrocene, and 1-bromo-2-fluoroferrocene. DFT calculations show that 1,2-dihaloferrocenes do not differ much in their highest occupied molecular orbital (HOMO) energies; however, their lowest unoccupied molecular orbital (LUMO) energies – and thus the HOMO/LUMO gaps – correlate with the sum of the halogen electronegativities. In addition, a synthesis of the rather sensitive 2-aminoferrocenecarboxylic acid, the ferrocene analogue of anthranilic acid, is presented, which starts from ferrocene-1,2-dicarboxylic acid. However, 2-aminoferrocenecarboxylic acid rapidly decomposed and thus could not be properly characterized. Ferrocene-1,2-dicarboxylic anhydride serves as the starting material for preliminary photochemical decarbonylation/decarboxylation experiments resulting in 1,2-dideuterioferrocene when carried out in [D8]toluene.
KW - Ferrocene
KW - Halogenation
KW - Iron
KW - Lithiation
KW - Sandwich complexes
UR - http://www.scopus.com/inward/record.url?scp=84988878612&partnerID=8YFLogxK
U2 - 10.1002/ejic.201600766
DO - 10.1002/ejic.201600766
M3 - Article
AN - SCOPUS:84988878612
VL - 2017
SP - 378
EP - 387
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 2
ER -