0000000001300202
AUTHOR
Torben Kienz
Anticancer Effect of an Electronically Coupled Oligoferrocene
The mode of anticancer activity of simple ferrocenes often relies on their intracellular oxidation with the formation of cytotoxic ferrocenium species. The former compounds should be considered as ...
Impact of O → S Exchange in Ferrocenyl Amides on the Structure and Redox Chemistry
The conformations and redox chemistry of ferrocenyl amides have been investigated in considerable depth in the last few years, while ferrocenyl thioamides have attracted less interest so far, although distinctly different conformations and reactivity patterns are expected. Monoferrocenyl amides Fc-NHC(O)CH3 (1) and 1,1′-CH3O(O)C-Fn-NHC(O)CH3 (2) and diferrocenyl amides Fc-NHC(O)-Fc (5) and Fc-NHC(O)-Fn-NHC(O)CH3 (6) are easily transformed into the corresponding thioamides (3, 4, 7, 8) by treatment with Lawesson’s reagent (2,4-bis(p-methoxyphenyl)-1,3-dithiaphosphetane-2,4-disulfide) (Fc = Fe(C5H4)(C5H5), Fn = Fe(C5H4)2). The thioamide conformations (cis/trans) in 3, 4, 7, and 8 and the hydr…
Generation and Oligomerization of N-Ferrocenyl Ketenimines via Open-Shell Intermediates
In the presence of oxidant (Ag[SbF6]) and base, N-ferrocenyl thioamide Fc-NHC(S)CH3 (H-1; Fc = Fe(η5-C5H5)(η5-C5H4)) converts in an unexpected multistep reaction sequence to a novel N,S-heterocyclic ring, which initiates an oligomerization reaction. Key intermediates toward the resulting complicated material are Ag6(1)6 silver clusters of the anionic N,S-chelating ligand 1− and EPR-active piano stool complexes resulting from ring-slipped cyclopentadienyl ligands, as well as electrophilic N-ferrocenyl ketenimine Fc-N═C═CH2 (2) and its ferrocenium cation 2•+ formed by hydrosulfide elimination. Mechanistic insight is achieved using X-ray diffraction and mass spectrometry, as well as EPR and NM…
Spin Trapping of Carbon-Centered Ferrocenyl Radicals with Nitrosobenzene
In contrast to metal centered 17 valence electron radicals, such as [Mn(CO)5]•, ferrocenium ions [Fe(C5H5)2]+ (1+), [Fe(C5Me5)2]+ (2+), [Fe(C5H5)(C5H4Et)]+ (3+), [Fe(C5H5)(C5H4NHC(O)Me)]+ (4+), and [Fe(C5H5)(C5H4NHC(S)Me)]+ (5+) do not add to nitrosobenzene PhNO to give metal-coordinated stable nitroxyl radicals. In the presence of the strong and oxidatively stable phosphazene base tert-butylimino-tris(dimethylamino)phosphorane, the quite acidic ferrocenium ions 1+–5+ are deprotonated to give a pool of transient and persistent radicals with different deprotonation sites [1–Hx]•–[5–Hx]•. One rather persistent iron-centered radical [4–HN]•, deprotonated at the nitrogen atom, has been detected…
CCDC 1475564: Experimental Crystal Structure Determination
Related Article: Torben Kienz, Christoph Förster, and Katja Heinze|2016|Organometallics|35|3681|doi:10.1021/acs.organomet.6b00619
CCDC 1993737: Experimental Crystal Structure Determination
Related Article: Gina Zeh, Philipp Haines, Matthias E. Miehlich, Torben Kienz, Andreas Neidlinger, Ralf P. Friedrich, Hülya G. Özkan, Christoph Alexiou, Frank Hampel, Dirk M. Guldi, Karsten Meyer, Jürgen Schatz, Katja Heinze, Andriy Mokhir|2020|Organometallics|39|3112|doi:10.1021/acs.organomet.0c00306
CCDC 978126: Experimental Crystal Structure Determination
Related Article: Torben Kienz, Christoph Förster, and Katja Heinze|2014|Organometallics|33|4803|doi:10.1021/om500052k
CCDC 1475563: Experimental Crystal Structure Determination
Related Article: Torben Kienz, Christoph Förster, and Katja Heinze|2016|Organometallics|35|3681|doi:10.1021/acs.organomet.6b00619
CCDC 1993738: Experimental Crystal Structure Determination
Related Article: Gina Zeh, Philipp Haines, Matthias E. Miehlich, Torben Kienz, Andreas Neidlinger, Ralf P. Friedrich, Hülya G. Özkan, Christoph Alexiou, Frank Hampel, Dirk M. Guldi, Karsten Meyer, Jürgen Schatz, Katja Heinze, Andriy Mokhir|2020|Organometallics|39|3112|doi:10.1021/acs.organomet.0c00306
CCDC 1484852: Experimental Crystal Structure Determination
Related Article: Torben Kienz, Christoph Förster, and Katja Heinze|2016|Organometallics|35|3681|doi:10.1021/acs.organomet.6b00619