Stable CAAC-Triazenes: A New Nitrogen Ligand System With Donor and Conformational Flexibility, and With Application...

N-heterocyclic imines such as pyridylidene amines impart high catalytic activity when coordinated to a transition metal, largely imposed by their electronic flexibility. Here, this donor flexibility has been applied for the first time to CAAC-based systems through the synthesis of CAAC-triazenes. These new ligands offer a larger π-conjugation that extends from the N-heterocyclic carbene through three nitrogens rather than just one, as observed in N-heterocyclic imines. We demonstrate the straightforward synthesis of three new CAAC-triazenes containing different substituents on the terminal triazene nitrogen. These compounds are remarkably stable up to 120 °C without loss of N₂ as typically observed with similar triazenes. E-to-Z isomerization within the triazene is instigated by UV light and is partially reversible dependent on the triazene substituent. The quinoline-substituted CAAC-triazene 1-Q has been applied as an L,L'-type ligand in the synthesis of [PdCl₂(1-Q)], [PdCl(Me)(1-Q)] and [Pd(Me)(H₂O(1-Q)]⁺. E-to-Z ligand isomerization also occurs when coordinated to PdCl₂, providing access to on-metal manipulation. The cationic complex [PdMe(H₂O)(1-Q)]⁺ is a precatalyst for oligomerization of ethylene to form initially 2-butene and subsequently linear and branched C₈-C₁₂ products from butene activation. Moreover, isomerization of 1-hexene takes place efficiently with exceptionally low catalyst loading (10 ppm) and up to 74,000 turnover numbers.