Details
| Original language | English |
|---|---|
| Pages (from-to) | 1139-1147 |
| Number of pages | 9 |
| Journal | Advanced Synthesis and Catalysis |
| Volume | 351 |
| Issue number | 7-8 |
| Publication status | Published - 12 May 2009 |
Abstract
An improved synthesis of [1.1]ferroce-nophane-1,12-dione (2) by oxidation of [1.1]ferroce-nophane with 2,3-dichloro-5,6-dicyano-p-benzoqui-none (DDQ) is presented. The syn conformer of dione 2 is structurally characterized. The compound undergoes various addition reactions at the bridging carbonyl groups. Attempts to add 1,1′-dilithioferro-cene result, however, in the diadduct 9, not in the symmetric trinuclear diol 8. Reaction of 2 with sodium cyclopentadienide in the presence of aluminium trichloride (A1C13) gives the respective difulvene 11 in excellent yield. The dynamic behavior of 11 is investigated by variable temperature 1H NMR measurements (VT-NMR). The cyclovoltammogram of 11 indicates two reversible oxidation steps. Reduction of difulvene 11 with lithium aluminium hydride (LiAlH4) results in the formation of [1.1]ferroce-nophane 12 with cyclopentadienyl anion substituents at either one of the two bridges. While attempts to generate a third ferrocene moiety by reaction with iron(II) choride (FeCl2) have failed so far, the formation of 12 is established by protonolysis and methyla-tion reactions.
Keywords
- Conformation, Ferrocene, Ferroceno-phane, Fulvenes, Variable temperature NMR
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Advanced Synthesis and Catalysis, Vol. 351, No. 7-8, 12.05.2009, p. 1139-1147.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - [1.1]Ferrocenophane-1,12-dione as a precursor of 1,12-di(cyclo-penta-2,4- dienylidene)-[1.1]ferrocenophane, a doubly bridged difulvene
AU - Garabatos-Perera, José Ramon
AU - Wartchow, Rudolf
AU - Butenschön, Holger
PY - 2009/5/12
Y1 - 2009/5/12
N2 - An improved synthesis of [1.1]ferroce-nophane-1,12-dione (2) by oxidation of [1.1]ferroce-nophane with 2,3-dichloro-5,6-dicyano-p-benzoqui-none (DDQ) is presented. The syn conformer of dione 2 is structurally characterized. The compound undergoes various addition reactions at the bridging carbonyl groups. Attempts to add 1,1′-dilithioferro-cene result, however, in the diadduct 9, not in the symmetric trinuclear diol 8. Reaction of 2 with sodium cyclopentadienide in the presence of aluminium trichloride (A1C13) gives the respective difulvene 11 in excellent yield. The dynamic behavior of 11 is investigated by variable temperature 1H NMR measurements (VT-NMR). The cyclovoltammogram of 11 indicates two reversible oxidation steps. Reduction of difulvene 11 with lithium aluminium hydride (LiAlH4) results in the formation of [1.1]ferroce-nophane 12 with cyclopentadienyl anion substituents at either one of the two bridges. While attempts to generate a third ferrocene moiety by reaction with iron(II) choride (FeCl2) have failed so far, the formation of 12 is established by protonolysis and methyla-tion reactions.
AB - An improved synthesis of [1.1]ferroce-nophane-1,12-dione (2) by oxidation of [1.1]ferroce-nophane with 2,3-dichloro-5,6-dicyano-p-benzoqui-none (DDQ) is presented. The syn conformer of dione 2 is structurally characterized. The compound undergoes various addition reactions at the bridging carbonyl groups. Attempts to add 1,1′-dilithioferro-cene result, however, in the diadduct 9, not in the symmetric trinuclear diol 8. Reaction of 2 with sodium cyclopentadienide in the presence of aluminium trichloride (A1C13) gives the respective difulvene 11 in excellent yield. The dynamic behavior of 11 is investigated by variable temperature 1H NMR measurements (VT-NMR). The cyclovoltammogram of 11 indicates two reversible oxidation steps. Reduction of difulvene 11 with lithium aluminium hydride (LiAlH4) results in the formation of [1.1]ferroce-nophane 12 with cyclopentadienyl anion substituents at either one of the two bridges. While attempts to generate a third ferrocene moiety by reaction with iron(II) choride (FeCl2) have failed so far, the formation of 12 is established by protonolysis and methyla-tion reactions.
KW - Conformation
KW - Ferrocene
KW - Ferroceno-phane
KW - Fulvenes
KW - Variable temperature NMR
UR - http://www.scopus.com/inward/record.url?scp=66149125581&partnerID=8YFLogxK
U2 - 10.1002/adsc.200800780
DO - 10.1002/adsc.200800780
M3 - Article
AN - SCOPUS:66149125581
VL - 351
SP - 1139
EP - 1147
JO - Advanced Synthesis and Catalysis
JF - Advanced Synthesis and Catalysis
SN - 1615-4150
IS - 7-8
ER -