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Redox‐Active N‐Heterocyclic Germylenes and Stannylenes with a Ferrocene‐1,1′‐diyl Backbone
Author(s) -
Oetzel Jan,
Weyer Nadine,
Bruhn Clemens,
Leibold Michael,
Gerke Birgit,
Pöttgen Rainer,
Maier Markus,
Winter Rainer F.,
Holthausen Max. C.,
Siemeling Ulrich
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605074
Subject(s) - ferrocene , chemistry , tin , redox , trimethylsilyl , decomposition , medicinal chemistry , stereochemistry , ion , polymer chemistry , crystallography , electrochemistry , organic chemistry , electrode
We describe ferrocene‐based N‐heterocyclic germylenes and stannylenes of the type [Fe{(η 5 ‐C 5 H 4 )NR} 2 E:] ( 1 R E; E=Ge, Sn; R=neopentyl (Np), mesityl (Mes), trimethylsilyl (TMS)), which constitute the first examples of redox‐functionalised N‐heterocyclic tetrylenes (NHTs). These compounds are thermally stable and were structurally characterised by means of X‐ray diffraction studies, except for the neopentyl‐substituted stannylene 1 Np Sn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH 2 t Bu)(N=CH t Bu)] ( 2 ) and the spiro tin(IV) compound ( 1 Np ) 2 Sn ( 3 ). DFT calculations show that the HOMO of the NHTs of our study is localised on the ferrocenylene backbone. A one‐electron oxidation process affords ions of the type 1 R E +. . In contrast to the NHC system 1 R C, the localised ferrocenium‐type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 R E +. .