Electronic structure of four-coordinate iron(I) complex supported by a bis(phosphaethenyl)pyridine ligand.

A 15-electron iron complex with a formal Fe(I) center, [FeBr(BPEP)] (BPEP = 2,6-bis(1-phenyl-2-phosphaethenyl)pyridine), was prepared by one-electron reduction of the dibromide precursor [FeBr(2)(BPEP)]. The single-crystal diffraction analysis revealed a distorted trigonal monopyramidal arrangement around the iron center, and SQUID magnetometry established the S = 3/2 ground state. The Mossbauer isomer shift value (delta = 0.59 mm/s) was consistent with a high-spin Fe(I) center of [FeBr(BPEP)]. DFT calculations for a model complex revealed two highly delocalized molecular orbitals formed by bonding and antibonding interactions between the d(z(2)) (Fe) and pi* (BPEP) orbitals. Orbital occupancy analysis demonstrated the electronic structure with a high-spin Fe(I) center. The effective dpi-ppi interaction between iron and BPEP was concluded to be responsible for the highly distorted structure of [FeBr(BPEP)], with its rather uncommon trigonal monopyramidal configuration.