A “Naked” FeIII-(O22–)-CuII Species Allows for Structural and Spectroscopic Tuning of Low-Spin Heme-Peroxo-Cu Complexes
† Johns Hopkins University, Baltimore, Maryland 21218, United States
‡ Department of Chemistry, Stanford University, Stanford, California 94305, United States
Abstract
Here we describe a new approach for the generation of heme-peroxo-Cu compounds, using a “naked” complex synthon, [(F8)FeIII-(O22–)-CuII(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 FeIII-(O22–)-CuII(L) complexes. These possess markedly varying CuII 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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