Triaminoalkenes Derived from Cyclic (Alkyl)(amino)carbenes with a 1,1′‐Ferrocenylene Backbone and N‐Heterocyclic Carbenes: fcCAAC–NHC Heterodimers
Suman Yadav, Clemens Bruhn, Clemens Lücke, Richard Rudolf, Tabea Pfister, Biprajit Sarkar, Ulrich Siemeling
TL;DR
This paper reports the synthesis and redox properties of new compounds combining ferrocene and N-heterocyclic carbenes, revealing multiple oxidation states.
Contribution
The novel contribution is the synthesis and characterization of fcCAAC–NHC heterodimers with unique redox behavior involving multiple oxidation states.
Findings
The compounds undergo two consecutive one-electron oxidations but the tricationic state is unstable.
The first oxidation occurs at the C=CN2 atom, while the second involves the Fe atom.
DFT calculations align with experimental results, showing radical formation in oxidation processes.
Abstract
The study addresses triaminoalkenes derived from [3]ferrocenophane‐type cyclic (alkyl)(amino)carbenes (fcCAACs) fc(CPh2—C—NR) (fc = 1,1′‐ferrocenylene) and N‐heterocyclic carbenes (NHCs). Stable target compounds are obtained in good yields as crystalline solids by the combination of [fc(CPh2—CH=NMe)][BF4] with N,N′‐dimethylimidazolin‐2‐ylidene and of [fc(CPh2—CH=N‐p‐C6H4‐tBu)](OTf) with 1,3,4,5‐tetramethylimidazolin‐2‐ylidene, respectively, followed by treatment of the resulting addition product with KN(SiMe3)2. Due to the presence of a triaminoethene unit and a ferrocene moiety, four redox states are expected for such fcCAAC–NHC heterodimers, viz., electroneutral, mono‐, di‐, and tricationic. An investigation of their redox behavior by electrochemical methods (cyclic voltammetry and differential pulse voltammetry) has revealed that these compounds undergo two consecutive one‐electron…
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Taxonomy
TopicsN-Heterocyclic Carbenes in Organic and Inorganic Chemistry · Catalytic Cross-Coupling Reactions · Synthetic Organic Chemistry Methods