Exploring Ligand-Centered Hydride and H-Atom Transfer

Abstract

The nickel(II) complex [ON(H)O]Ni(PPh₃) ([ON(H)O]^2- = bis(3,5-di-tert-butyl-2-phenoxy)amine), bearing a protonated redox-active ligand, was examined for its ability to serve as a hydrogen atom (H^•) and hydride (H^-) donor. Deprotonation of [ON(H)O]Ni(PPh₃) afforded the square-planar anion {[ONO^cat]Ni(PPh₃)}^1-, whereas hydrogen atom transfer from [ON(H)O]Ni(PPh₃) to TEMPO^• in the presence of added PPh₃ afforded five-coordinate [ONO]Ni(PPh₃)₂ that has been structurally characterized. In solution, this five-coordinate complex exists in equilibrium with four-coordinate [ONO]Ni(PPh₃), and this ligand exchange equilibrium correlates with a valence tautomerization between the redox-active ligand and the nickel center. Abstraction of a hydride from [ON(H)O]Ni(PPh₃) in the presence of PPh₃ afforded the octahedral complex, [ONO^q]Ni(OTf)(PPh₃)₂, which was characterized as an S = 1, nickel(II) complex. Bond dissociation free energy (BDFE) and hydricity (ΔG°_H-) measurements benchmark the thermodynamic propensity of this complex to participate in ligand-centered H^• and H^- transfer reactions.