A "Naked" Fe-III-(O-2(2-))-Cu-II Species Allows for Structural and Spectroscopic Tuning of Low-Spin Heme-Peroxo-Cu Complexes

作者：Garcia Bosch Isaac; Adam Suzanne M; Schaefer Andrew W; Sharma Savita K; Peterson Ryan L; Solomon Edward I^*; Karlin Kenneth D

来源：Journal of the American Chemical Society, 2015, 137(3): 1032-1035.

DOI：10.1021/ja5115198

Here we describe a new approach for the generation of heme-peroxo-Cu compounds, using a naked complex synthon, [(F8)FeIII-(O-2(2-))-Cu-II(MeTHF)(3)](+) (MeTHF = 2-methyltetrahydrofuran; F-8 = 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-(O-2(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.

• 出版日期2015-1-28