A Strongly Ambiphilic Ferrocene‐Based Cyclic (Alkyl)(amino)carbene – Specific Decomposition to an Enamine by a 1,2‐Phenyl Shift

The recently described crystalline cyclic (alkyl)(amino)carbene with a 1,1’‐ferrocenylene (fc) backbone fc(CPh₂−C−NMes) (A, Mes=mesityl) is highly reactive due to its particularly pronounced ambiphilicity and is thermally not stable in solution due to an intramolecular insertion of the divalent carbon atom into a methyl C−H bond of the Mes substituent. The closely related congener fc(CPh₂−C−N‐p‐C₆H₄‐tBu) (1) cannot undergo such an insertion reaction. Nevertheless, 1 is too short‐lived for isolation due to a rapid 1,2‐shift of a phenyl group, furnishing the isomeric cyclic enamine fc[C(Ph)=C(Ph)−N‐p‐C₆H₄‐tBu] (1’) in a specific decomposition process unprecedented for CAACs. Trapping of 1 was possible with carbon monoxide, elemental selenium and with [CuBr(SMe₂)], respectively affording the aminoketene 1=C=O, the selenoamide 1=Se and the homoleptic Cu^I complex [Cu(1)₂][CuBr₂]. 1 is an even stronger ambiphile than A according to NMR spectroscopic data. Similar to A, 1 does not react with H₂, because the experimentally observed intramolecular process is kinetically more favourable according to DFT results.