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Synthesis and Catalysis of Redox‐Active Bis(imino)acenaphthene (BIAN) Iron Complexes
Author(s) -
Villa Matteo,
Miesel Dominique,
Hildebrandt Alexander,
Ragaini Fabio,
Schaarschmidt Dieter,
Jacobi von Wangelin Axel
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201700144
Subject(s) - acenaphthene , chemistry , redox , ligand (biochemistry) , catalysis , octahedron , ferrocene , medicinal chemistry , stereochemistry , crystallography , photochemistry , electrochemistry , inorganic chemistry , crystal structure , organic chemistry , biochemistry , receptor , electrode , anthracene
Reactions of various substituted bis(imino)acenaphthenes (R‐BIANs) with FeCl 2 (thf) 1.5 afforded the tetrahedral complexes (R‐BIAN)FeCl 2 ( 2 ) from bulky α‐diimines and the octahedral complexes [Fe(R‐BIAN) 3 ][FeCl 4 ] 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 Fe II center. The two sets of complexes exhibit distinct charge‐transfer band intensities and redox activities. (R‐BIAN)FeCl 2 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.