Abstract
The reactivity of the all-ferrous FeN heterocubane [Fe4(Ntrop)4] (1) with i)Brønsted acids, ii)σ-donors, iii)σ-donors/π-acceptors, and iv)one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(μ3-imido) 48 electron complex in the former case and a tetranuclear all ferric μ-oxo-μ-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 15797-15805 |
| Number of pages | 9 |
| Journal | Chemistry - A European Journal |
| Volume | 21 |
| Issue number | 44 |
| DOIs | |
| State | Published - Oct 1 2015 |
| Externally published | Yes |
Fingerprint
All Science Journal Classification (ASJC) codes
- Catalysis
- Organic Chemistry
Keywords
- cluster compounds
- heterocubanes
- iron
- oxidation
- reduction
Cite this
}
Reactivity of an All-Ferrous Iron-Nitrogen Heterocubane under Reductive and Oxidative Conditions. / Lichtenberg, Crispin; Prokopchuk, Demyan E.; Adelhardt, Mario; Viciu, Liliana; Meyer, Karsten; Grützmacher, Hansjörg.
In: Chemistry - A European Journal, Vol. 21, No. 44, 01.10.2015, p. 15797-15805.Research output: Contribution to journal › Article
TY - JOUR
T1 - Reactivity of an All-Ferrous Iron-Nitrogen Heterocubane under Reductive and Oxidative Conditions
AU - Lichtenberg, Crispin
AU - Prokopchuk, Demyan E.
AU - Adelhardt, Mario
AU - Viciu, Liliana
AU - Meyer, Karsten
AU - Grützmacher, Hansjörg
PY - 2015/10/1
Y1 - 2015/10/1
N2 - The reactivity of the all-ferrous FeN heterocubane [Fe4(Ntrop)4] (1) with i)Brønsted acids, ii)σ-donors, iii)σ-donors/π-acceptors, and iv)one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(μ3-imido) 48 electron complex in the former case and a tetranuclear all ferric μ-oxo-μ-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.
AB - The reactivity of the all-ferrous FeN heterocubane [Fe4(Ntrop)4] (1) with i)Brønsted acids, ii)σ-donors, iii)σ-donors/π-acceptors, and iv)one-electron oxidants has been investigated (trop = 5H-dibenzo[a,d]cyclo-hepten-5-yl). 1 showed self-re-assembling after reactions with i) and proved surprisingly inert in reactions with ii) and iii), with the exception of CO. Reductive and oxidative cluster degradation was observed in reactions with CO and TEMPO, respectively. These reactions yielded new cluster compounds, namely a trinuclear bis(μ3-imido) 48 electron complex in the former case and a tetranuclear all ferric μ-oxo-μ-imido species in the latter case. Characterization techniques include NMR and in situ IR spectroscopy, single crystal X-ray analysis, Mössbauer spectroscopy, cyclic voltammetry, magnetic susceptibility measurements, and DFT calculations.
KW - cluster compounds
KW - heterocubanes
KW - iron
KW - oxidation
KW - reduction
UR - http://www.scopus.com/inward/record.url?scp=84945472032&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84945472032&partnerID=8YFLogxK
U2 - https://doi.org/10.1002/chem.201502530
DO - https://doi.org/10.1002/chem.201502530
M3 - Article
VL - 21
SP - 15797
EP - 15805
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 44
ER -