title: A "naked" Fe(III)-(O₂²⁻)-Cu(II) species allows for structural and spectroscopic tuning of low-spin heme-peroxo-Cu complexes.
abstract: Here we describe a new approach for the generation of heme-peroxo-Cu compounds, using a "naked" complex synthon, [(F8)Fe(III)-(O2(2-))-Cu(II)(MeTHF)3](+) (MeTHF = 2-methyltetrahydrofuran; F8 = tetrakis(2,6-difluorophenyl)porphyrinate). Addition of varying ligands (L) for Cu allows the generation and spectroscopic characterization of a family of high- and low-spin Fe(III)-(O2(2-))-Cu(II)(L) complexes. These possess markedly varying Cu(II) coordination geometries, leading to tunable Fe-O, O-O, and Cu-O bond strengths. DFT calculations accompanied by vibrational data correlations give detailed structural insights.
authors.affiliation: Johns Hopkins University , Baltimore, Maryland 21218, United States.
authors.forename: Isaac
authors.initials: I
authors.lastname: Garcia-Bosch
authors.forename: Suzanne M
authors.initials: SM
authors.lastname: Adam
authors.forename: Andrew W
authors.initials: AW
authors.lastname: Schaefer
authors.forename: Savita K
authors.initials: SK
authors.lastname: Sharma
authors.forename: Ryan L
authors.initials: RL
authors.lastname: Peterson
authors.forename: Edward I
authors.initials: EI
authors.lastname: Solomon
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D006418:Heme / Q000737:chemistry*; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D005296:Ferrous Compounds; D006418:Heme; D003300:Copper; D010100:Oxygen