Using internal electrostatic fields to manipulate the valence manifolds of copper complexes

A series of tetradentate tris(phosphinimine) ligands (^R3P₃tren) was developed and bound to Cu^I to form the trigonal pyramidal, C_3v-symmetric cuprous complexes [^R3P₃tren-Cu][BAr^F₄] (1PR3) (PR₃ = PMe₃, PMe₂Ph, PMePh₂, PPh₃, PMe₂(NEt₂), BAr^F₄ = B(C₆F₅)₄). Electrochemical studies on the Cu^I complexes were undertaken, and the permethylated analog, 1PMe3, was found to display an unprecedentedly cathodic Cu^I/Cu^II redox potential (−780 mV vs. Fc/Fc⁺ in isobutyronitrile). Elucidation of the electronic structures of 1PR3via density functional theory (DFT) studies revealed atypical valence manifold configurations, resulting from strongly σ-donating phosphinimine moieties in the xy-plane that destabilize 2e (d_xy/d_x²−y²) orbital sets and uniquely stabilized a₁ (d_z²) orbitals. Support is provided that the a₁ stabilizations result from intramolecular electrostatic fields (ESFs) generated from cationic character on the phosphinimine moieties in ^R3P₃tren. This view is corroborated via 1-dimensional electrostatic potential maps along the z-axes of 1PR3 and their isostructural analogues. Experimental validation of this computational model is provided upon oxidation of 1PMe3 to the cupric complex [^Me3P₃tren-Cu][OTf]₂ (2PMe3), which displays a characteristic Jahn–Teller distortion in the form of a see-saw, pseudo-C_s-symmetric geometry. A systematic anodic shift in the potential of the Cu^I/Cu^II redox couple as the steric bulk in the secondary coordination sphere increases is explained through the complexes'' diminishing ability to access the ideal C_s-symmetric geometry upon oxidation. The observations and calculations discussed in this work support the presence of internal electrostatic fields within the copper complexes, which subsequently influence the complexes'' properties via a method orthogonal to classic ligand field tuning.

Secondary coordination sphere electrostatic effects tune the valence manifolds of copper centers, impacting molecular geometries, photophysical properties, and redox potentials.