Abstract
The unusual dinucleating properties of a simple bidentate Schiff base (LH, 1) in the presence of weakly coordinating methanol solvent lead to the self-assembly of [ Fe 2 II ( L b ) 2 ( L t ) 2 ( μ - MeOH ) ] ( 2) ( b and t refer to bridging and terminally bound ligands, respectively). Complex 2 is the first diiron(II) species in which the two metal centers are triply bridged by single atoms in an asymmetric fashion, involving both μ-O Ph and μ-OH Me bridges. This binding mode produces an Fe⋯Fe distance of 3.139(1) Å. Dinucleation appears to be driven by a combination of ligand deficiency and solvent-mediated chemistry reminiscent of host–guest interactions. The presence of a μ-MeOH ligand is unprecedented in iron chemistry. Parallel-mode EPR spectra of complex 2 recorded at 4 K show an intense negative signal at g ∥ ≈ 16 , suggesting the dimeric form exists in solution.
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