Uncovering Redox Non-innocent Hydrogen-Bonding in Cu(I)-Diazene Complexes

The life-sustaining reduction of N₂ to NH₃ is thermoneutral yet kinetically challenged by high-energy intermediates such as N₂H₂. Exploring intramolecular H-bonding as a potential strategy to stabilize diazene intermediates, we employ a series of [TpCu]₂(μ-N₂H₂) complexes that exhibit H-bonding between pendant aromatic N-heterocycles (^xHet) such as pyridine and a bridging trans-N₂H₂ ligand at copper(I) centers. X-ray crystallography and IR spectroscopy clearly reveal H-bonding in [^pyMeTpCu]₂(μ-N₂H₂) while low-temperature ¹H NMR studies coupled with DFT analysis reveals a dynamic equilibrium between two closely related, symmetric H-bonded structural motifs. Importantly, the ^xHet pendant negligibly influences the electronic structure of TpCu^I centers in TpCu(CNAr^2,6-Me) complexes that lack H-bonding as judged by nearly indistinguishable ν(CN) frequencies (2113-2117 cm^-1). Nonetheless, H-bonding in the corresponding [TpCu]₂(μ-N₂H₂) complexes results in marked changes in ν(NN) (1398-1419 cm^-1) revealed through resonance Raman studies. Due to the closely matched N-H BDEs of N₂H₂ and the pyH⁰ cation radical, the aromatic N-heterocyclic pendants may encourage partial H-atom transfer (HAT) from N₂H₂ to ^xHet through redox-non-innocent H-bonding in [TpCu]₂(μ-N₂H₂). DFT studies reveal modest thermodynamic barriers for concerted transfer of both H-atoms of coordinated N₂H₂ to the ^xHet pendants to generate tautomeric [TpCu]₂(μ-N₂) complexes, identifying metal-assisted concerted dual HAT as a thermodynamically favorable pathway for N₂/N₂H₂ interconversion.