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  • Title: A "naked" Fe(III)-(O₂²⁻)-Cu(II) species allows for structural and spectroscopic tuning of low-spin heme-peroxo-Cu complexes.
    Author: Garcia-Bosch I, Adam SM, Schaefer AW, Sharma SK, Peterson RL, Solomon EI, Karlin KD.
    Journal: J Am Chem Soc; 2015 Jan 28; 137(3):1032-5. PubMed ID: 25594533.
    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.
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