Butadienyl Diiron Complexes: Nonplanar Metalla-Aromatics Involving σ-Type Orbital Overlap

A new class of nonplanar metalla-aromatics, diiron complexes bridged by a 1,3-butadienyl dianionic ligand, were synthesized in high yields from dilithio reagents and two equivalents of FeBr₂ . The complexes consist of two antiferromagnetically coupled high-spin Fe^II centers, as revealed by magnetometry, Mössbauer spectroscopy, and DFT calculations. Furthermore, experimental (X-ray structural analysis) and theoretical analyses (NICS, ICSS, AICD, MOs) suggest that the complexes are aromatic. Remarkably, this nonplanar metalla-aromaticity is achieved by an uncommon σ-type overlap between the ligand p and metal d orbitals, in sharp contrast to the intensively studied planar aromatic systems featuring delocalized π-type bonding. Specifically, the σ-type interaction between the two Fe 3d_xz orbitals and the butadienyl π orbital results in the formation of a six-electron conjugated system and hence enables the aromatic character.