Multielectron Redox Chemistry of Transition Metal Complexes Supported by a Non‐Innocent N3P2 Ligand: Synthesis, Characterization, and Catalytic Properties
European Journal of Inorganic Chemistry
A new redox‐active, diarylamido‐based ligand (LN3P2) capable of κ5‐N,N,N,P,P chelation has been used to prepare a series of complexes with the general formula [MII(LN3P2)]X, where M = Fe (1; X = OTf), Co (2; X = ClO4), or Ni (3; X = ClO4). The diarylamido core of monoanionic LN3P2 is derived from bis(2‐amino‐4‐methylphenyl)amine, which undergoes condensation with two equivalents of 2‐(diphenylphosphanyl)benzaldehyde to provide chelating arms with both arylphosphine and imine donors. X‐ray structural, magnetic, and spectroscopic studies indicate that the N3P2 coordination environment generally promotes low‐spin configurations. Three quasi‐reversible redox couples between +1.0 and –1.5 V (vs. Fc+/Fc) were observed in voltammetric studies of each complex, corresponding to MII/MIII oxidation, LN3P2‐based oxidation, and MII/MI reduction (in order of highest to lowest potential). Spectroscopic and computational analyses of 3ox – generated via chemical one‐electron oxidation of 3 – revealed that a stable diarylaminyl radical (LN3P2·) is formed upon oxidation. The ability of the CoII complex (2) to function as an electrocatalyst for H2 generation was evaluated in the presence of weak acids. Moderate activity was observed using 4‐tert‐butylphenol as the proton source at potentials below –2.0 V. The insights gained here will assist in the future design of pentadentate mixed N/P‐based chelates for catalytic processes.
Wang, Denan; Ekanayake, Danushka M.; Lindeman, Sergey V.; Verani, Cláudio N.; and Fiedler, Adam T., "Multielectron Redox Chemistry of Transition Metal Complexes Supported by a Non‐Innocent N3P2 Ligand: Synthesis, Characterization, and Catalytic Properties" (2018). Chemistry Faculty Research and Publications. 960.
ADA accessible version
Accepted version. European Journal of Inorganic Chemistry, Vol. 2018, No. 37 (October 9, 2018): 4133-4141. DOI. © 2018 John Wiley & Sons, Inc. Used with permission.