title: Correlation between the FeNO angle and d-p mixing in {FeNO}7 complexes.
abstract: The great majority of low-spin {FeNO}(7) complexes exhibit FeNO angles of around 140-145°, whereas a small handful are characterized by linear FeNO units. Conspicuously absent are intermediate FeNO angles of 150-170°. Spurred by the recent observation of such an angle in a square-pyramidal {FeNO}(7) complex, we carried out a density functional theory survey of 12 additional, largely hypothetical complexes with porphyrin and corrole analogues as equatorial ligands. Our calculations predict several instances of intermediate FeNO angles. The calculations further indicate a strong, positive correlation (R(2) = 0.9) between the FeNO angle and metal p character in the Fe d(z(2))-based highest occupied molecular orbital.
authors.affiliation: Department of Chemistry and Center for Theoretical and Computational Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
authors.forename: Jeanet
authors.initials: J
authors.lastname: Conradie
authors.forename: Abhik
authors.initials: A
authors.lastname: Ghosh