Details
| Original language | English |
|---|---|
| Pages (from-to) | 13132-13139 |
| Number of pages | 8 |
| Journal | ChemistrySelect |
| Volume | 3 |
| Issue number | 46 |
| Publication status | Published - 10 Dec 2018 |
Abstract
1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’-di(2-tert-butylphosphanylethyl)ferrocene followed by treatment with 1,1’-di(2-bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature-dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91<T<236 K. The metal atom vibrational amplitudes as a function of temperature have been determined for 1,16-di-tert-butyl-1,16-diphospha[5.5]ferrocenophane as well as for the diamagnetic site in the monooxidation product.
Keywords
- Diphosphane, Ferrocenium, Ferrocenophane, Mössbauer spectroscopy
ASJC Scopus subject areas
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In: ChemistrySelect, Vol. 3, No. 46, 10.12.2018, p. 13132-13139.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane
T2 - Synthesis, Reactions and Mössbauer Spectroscopy
AU - Werner, Irina
AU - Heinisch, Sandra Lauren
AU - Nowik, Israel
AU - Herber, Rolfe H.
AU - Butenschön, Holger
N1 - Funding information: This work was generously supported by the Deutsche Forschungsgemeinschaft (BU 814/20-1, BU 814/20-2). We thank Ms. Katharina Nolte for help with the DTA/TG measurement.
PY - 2018/12/10
Y1 - 2018/12/10
N2 - 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’-di(2-tert-butylphosphanylethyl)ferrocene followed by treatment with 1,1’-di(2-bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature-dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91<T<236 K. The metal atom vibrational amplitudes as a function of temperature have been determined for 1,16-di-tert-butyl-1,16-diphospha[5.5]ferrocenophane as well as for the diamagnetic site in the monooxidation product.
AB - 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’-di(2-tert-butylphosphanylethyl)ferrocene followed by treatment with 1,1’-di(2-bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16-Di-tert-butyl-1,16-diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature-dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91<T<236 K. The metal atom vibrational amplitudes as a function of temperature have been determined for 1,16-di-tert-butyl-1,16-diphospha[5.5]ferrocenophane as well as for the diamagnetic site in the monooxidation product.
KW - Diphosphane
KW - Ferrocenium
KW - Ferrocenophane
KW - Mössbauer spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85058675425&partnerID=8YFLogxK
U2 - 10.1002/slct.201802793
DO - 10.1002/slct.201802793
M3 - Article
AN - SCOPUS:85058675425
VL - 3
SP - 13132
EP - 13139
JO - ChemistrySelect
JF - ChemistrySelect
SN - 2365-6549
IS - 46
ER -