Redox-Active N-Heterocyclic Germylenes and Stannylenes with a Ferrocene-1,1'-diyl Backbone.
Redox-Active N-Heterocyclic Germylenes and Stannylenes with a Ferrocene-1,1'-diyl Backbone.
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DOI：
10.1002/chem.201605074
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发表时间：
2017-01
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通讯作者：
J. Oetzel;Nadine Weyer;C. Bruhn;Michael Leibold;Birgit Gerke;R. Pöttgen;Markus A. Maier;R. Winter;M. C. Holthausen;U. Siemeling
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文献类型：
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作者：
J. Oetzel;Nadine Weyer;C. Bruhn;Michael Leibold;Birgit Gerke;R. Pöttgen;Markus A. Maier;R. Winter;M. C. Holthausen;U. Siemeling
我们描述了[Fe{(η5 -C5 H4)NR}2 E:] (1 RE； E=Ge, Sn； R=neopentyl (Np), mesityl （Mes), trimethylsilyl (TMS)）类型的二茂铁基n -杂环四烯和锡烯，它们构成了氧化还原功能化n -杂环四烯（NHTs）的第一个例子。这些化合物都是热稳定的，并通过x射线衍射研究进行了结构表征，除了新戊基取代的锡炔1 NpSn，其分解得到氨基亚铁二茂物[fc(NHCH2 tBu)(N=CHtBu)](2)和螺旋锡（IV）化合物（1 Np）2 Sn(3)。DFT计算表明，我们研究的nht的HOMO定位在二茂铁骨架上。单电子氧化过程产生1型RE+离子。与NHC体系1rc相比，氧化形式的局部二茂铁型性质不会损害1re +的基本四烯性质。
We describe ferrocene-based N-heterocyclic germylenes and stannylenes of the type [Fe{(η5 -C5 H4 )NR}2 E:] (1 RE; 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 NpSn, the decomposition of which afforded the aminoiminoferrocene [fc(NHCH2 tBu)(N=CHtBu)] (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 RE+. . In contrast to the NHC system 1 RC, the localised ferrocenium-type nature of the oxidised form does not compromise the fundamental tetrylene character of 1 RE+. .