Cross‐Coupling Reactions between Stable Carbenes

Abstract

By utilizing stable carbenes with low-lying LUMOs, coupling with the stable nucleophilic diaminocyclopropenylidene was achieved. This reaction resulted in the formation of two new and rare examples of a bent allene as well as the isolation of the first carbene-carbene heterodimer.

Aromaticity and sterics control whether a cationic olefin radical is resistant to disproportionation

“…[38][39][40][41] Other investigations explored complementary synthetic approaches [42][43][44][45] or focused on other heterocycles as building blocks. [46][47][48] In combination with further related reports, [49][50][51][52] a considerable variety of such two-stage redox systems are now available. For applications as organic materials, it is highly desirable to predict or at least rationalize the redox potentials of these scaffolds.…”

Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments

“…Note that several carbene homodimers are known, but only af ew heterodimers have been isolated (36), because most of them are unstable as exemplified by 37,w hich rearranges into allene 38. [99] Since the pioneering work by Creutz and Taube, [100] bimetallic mixed-valence systems have attracted much attention. Although organic mixed-valence compounds have been known for decades,t heir applications have been hampered due to their sensitivity to oxygen and lack of thermal stability.…”

Cyclische Alkylaminocarbene (CAACs): Neues von guten Bekannten

“…Bemerkenswert ist, dass die Oxidation von 35 (−0.01 und +0.33 V gegen die Kalomelelektrode (SCE)) bei kleineren Potentialen als jene von TTF (+0.32 und +0.71 V gegen SCE) erfolgt. Außerdem sollte berücksichtigt werden, dass zwar mehrere Homodimere der Carbene bekannt sind, aber nur wenige Heterodimere bislang isoliert wurden ( 36 ), da ihre Instabilität, beispielsweise im Fall von 37 , durch Umlagerung zu Allenen 38 führt …”