Computational Investigation of the Metal and Ligand Substitution Effects on the Structure and Electronic States of the Phosphoranimide Tetramer Complexes of Cu(I), Ni(I), Co(I), and Fe(I).

The structurally unique saddle-shaped paramagnetic tetrametallic clusters of Co(I) and Ni(I) with phosphoranimide ligands have been synthesized and proposed as catalyst precursors. The analogous Cu(I) nanocluster is planar and diamagnetic. These notable variations in geometry and ground electronic states indicate that the effect of metal and ligand substituents on the structure and electronic properties of these complexes requires investigation. We present a computational study of a series of these novel homoleptic complexes containing Co(I), Ni(I), and Cu(I) as well as Fe(I) coordinated to phosphoranimides with electron-donating and withdrawing substituents, conducted at the relativistic density functional theory level using ZORA-PBE/TZP. The optimized structures of the saddle-shaped Co(I) and Ni(I) and planar Cu(I) tetramers with linear N-M-N coordination are validated with respect to X-ray diffraction determinations. The ground-state analysis indicates that Cu(I) complexes are diamagnetic, whereas Ni(I) and Co(I) complexes are in high-spin states, in agreement with magnetic susceptibility measurements. The computational results show that Fe(I) complexes are saddle shaped and high spin. The Co(I) complex is stabilized by a metal macrocycle distortion from square to diamond, as elucidated from its Walsh diagram. The effects of metals and ligand substituents on the ground electronic state, metal center coordination environment, and energy of the complexes are investigated. The bulky tertiary butyl substituent causes the largest saddle-shape distortion of the tetramer marcocycle, which partially offsets its electron-donating effect. Macrocycle distortions with N-M-N site angles ranging from obtuse to alternating obtuse reflex are correlated with the increasing number of unpaired electrons. The phenyl-substituted complexes are expected to have the highest reactivity toward electrophiles. Understanding the interplay between structural and electronic parameters is intended to guide the development of synthetic cooperative systems for multielectron redox reactions, models of biological systems, and molecular magnets.