Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

The tris(phosphinoamide)-bridged Fe(II)Fe(II) diiron complex Fe(μ-(i)PrNPPh2)3Fe(η(2)-(i)PrNPPh2) (1) can be reduced in the absence or presence of PMe3 to generate the mixed-valence Fe(II)Fe(I) complexes Fe(μ-(i)PrNPPh2)3Fe(PPh2NH(i)Pr) (2) or Fe(μ-(i)PrNPPh2)3Fe(PMe3) (3), respectively. Following a typical oxidative group transfer procedure, treatment of 2 or 3 with organic azides generates the mixed-valent Fe(II)Fe(III) imido complexes Fe((i)PrNPPh2)3Fe≡NR (R = (t)Bu (4), Ad (5), 2,4,6-trimethylphenyl (6)). These complexes represent the first examples of first-row bimetallic complexes featuring both metal-ligand multiple bonds and metal-metal bonds. The reduced complexes 2 and 3 and imido complexes 4-6 have been characterized via X-ray crystallography, Mössbauer spectroscopy, cyclic voltammetry, and SQUID magnetometry, and a theoretical description of the bonding within these diiron complexes has been obtained using computational methods. The effect of the metal-metal interaction on the electronic structure and bonding in diiron imido complexes 4-6 is discussed in the context of similar monometallic iron imido complexes.