Journal article

Structures, Spectroscopic Properties, and Dioxygen Reactivity of 5-and 6-Coordinate Nonheme Iron(11) Complexes: A Combined Enzyme/Model Study of Thiol Dioxygenases

Jesse B Gordon, Jeremy P McGale, Joshua R Prendergast, Zahra Shirani-Sarmazeh, Maxime A Siegler, Guy NL Jameson, David P Goldberg

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | AMER CHEMICAL SOC | Published : 2018

Abstract

The synthesis of four new FeII(N4S(thiolate)) complexes as models of the thiol dioxygenases are described. They are composed of derivatives of the neutral, tridentate ligand triazacyclononane (R3TACN; R = Me, iPr) and 2-aminobenzenethiolate (abtx; X = H, CF3), a non-native substrate for thiol dioxygenases. The coordination number of these complexes depends on the identity of the TACN derivative, giving 6-coordinate (6-coord) complexes for FeII(Me3TACN)(abtx)(OTf) (1: X = H; 2: X = CF3) and 5-coordinate (5-coord) complexes for [FeII(iPr3TACN)(abtx)](OTf) (3: X = H; 4: X = CF3). Complexes 1-4 were examined by UV-vis, 1H/19F NMR, and Mössbauer spectroscopies, and density functional theory (DFT)..

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University of Melbourne Researchers

Grants

Awarded by NIH


Awarded by NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES


Funding Acknowledgements

The NIH (GM119374 to D.P.G.) is gratefully acknowledged for financial support. G.N.L.J. further thanks the Faculty of Science, the University of Melbourne for financial support. J.PM. is thankful for funding from the Johns Hopkins University Dean's Undergraduate Research Award and Provost's Undergraduate Research Award. Computer time was provided by the Maryland Advanced Research Computing Center (MARCC).