Comparing the Ligand Behavior of N-Heterocyclic Phosphenium and Nitrosyl Units in Iron and Chromium Complexes

N-Heterocyclic phosphenium (NHP) and nitrosonium (NO⁺) ligands are often viewed as isolobal analogues that share the capability to switch between different charge states and thus display redox "noninnocent" behavior. We report here on mixed complexes [(NHP)M(CO) _n(NO)] (M = Fe, Cr; n = 2, 3), which permit evaluating the donor/acceptor properties of both types of ligands and their interplay in a single complex. The crystalline target compounds were obtained from reactions of N-heterocyclic phosphenium triflates with PPN[Fe(CO)₃(NO)] or PPN[Cr(CO)₄(NO)], respectively, and fully characterized (PPN = nitride-bistriphenylphosphonium cation). The structural and spectroscopic (IR, UV-vis) data support the presence of carbene-analogue NHP ligands with an overall positive charge state and π-acceptor character. Even if the structural features of the M-NO unit were in all but one product blurred by crystallographic CO/NO disorder, spectroscopic studies and the structural data of the remaining compound suggest that the NO units exhibit nitroxide (NO^-) character. This assignment was validated by computational studies, which reveal also that the electronic structure of iron NHP/NO complexes is closely akin to that of the Hieber anion, [Fe(CO)₃(NO)]^-. The electrophilic character of the NHP units is further reflected in the chemical behavior of the mixed complexes. Cyclic voltammetry and IR-SEC studies revealed that complex [(NHP)Fe(CO)₂(NO)] (4) undergoes chemically reversible one-electron reduction. Computational studies indicate that the NHP unit in the resulting product carries significant radical character, and the reduction may thus be classified as predominantly ligand-centered. Reaction of 4 with sodium azide proceeded likewise under nucleophilic attack at phosphorus and decomplexation, while super hydride and methyl lithium reacted with all chromium and iron complexes via transfer of a hydride or methyl anion to the NHP unit to afford anionic phosphine complexes. Some of these species were isolated after cation exchange or trapped with electrophiles (H⁺, SnPh₃⁺) to afford neutral complexes representing the products of a formal hydrogenation or hydrostannylation of the original M═P double bond.