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- Title
Synthesis and Catalysis of Redox-Active Bis(imino)acenaphthene (BIAN) Iron Complexes.
- Authors
Villa, Matteo; Miesel, Dominique; Hildebrandt, Alexander; Ragaini, Fabio; Schaarschmidt, Dieter; Jacobi von Wangelin, Axel
- Abstract
Reactions of various substituted bis(imino)acenaphthenes (R-BIANs) with FeCl2(thf)1.5 afforded the tetrahedral complexes (R-BIAN)FeCl2 ( 2) from bulky α-diimines and the octahedral complexes [Fe(R-BIAN)3][FeCl4]2 ( 3) from less bulky ligands. The driving force for the formation of complexes 3 is the high ligand-field stabilization of the low-spin FeII center. The two sets of complexes exhibit distinct charge-transfer band intensities and redox activities. (R-BIAN)FeCl2 complexes showed reversible ligand-centered reductions at −0.9 V (vs. FcH/FcH+; FcH: ferrocene); further reduction led to decomposition. Irreversible oxidations were observed at 0.2 and 0.4 V, associated with a reduction at −0.4 V, as well as a ligand-centered redox event at 1.0 V. First applications of the Fe(BIAN) complexes to hydrogenations of alkenes indicated good catalytic activity under mild conditions.
- Subjects
ACENAPHTHENE; OXIDATION-reduction reaction; IMINO compounds; CATALYTIC activity; CHEMICAL decomposition; IRON chlorides; HYDROGENATION
- Publication
ChemCatChem, 2017, Vol 9, Issue 16, p3203
- ISSN
1867-3880
- Publication type
Article
- DOI
10.1002/cctc.201700144