Bis[cyclic (alkyl)(amino)carbene] isomers: Stable trans-bis(CAAC) versus facile olefin formation for cis-bis(CAAC)

Isomeric bis(aldiminium) salts with a 1,4-cyclohexylene framework were synthesized. The first isolable bis(CAAC) was prepared from the trans-stereoisomer and its ditopic ligand competency was proven by conversion to iridium(i) and rhodium(i) complexes. Upon deprotonation, the cis-isomer yielded an electron rich olefin via a classic, proton-catalyzed pathway. The CC bond formation from the desired cis-bis(CAAC) was shown to be thermodynamically very favorable and to involve a small activation barrier. Compounds that can be described as insertion products of the cis-bis(CAAC) into the E–H bonds of NH3, CH3CN and H2O were also identified.