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Communication

Mechanistic Studies of Hangman Salophen-Mediated Activation of O−O Bonds

Supporting Info

Shih-Yuan Liu,^† Jake D. Soper,^† Jenny Y. Yang,^† Elena V. Rybak-Akimova,^‡ and Daniel G. Nocera*^†

Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, and Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155

Inorg. Chem., 2006, 45 (19), pp 7572–7574

DOI: 10.1021/ic0602087

Publication Date (Web): August 16, 2006

†

Massachusetts Institute of Technology.

‡

Tufts University.

To whom correspondence should be addressed. E-mail: nocera@mit.edu.

Abstract

Stopped-flow kinetic studies of a HSX−Mn−SalophOMe (1) catalyst provide spectroscopic evidence for the direct generation of a manganese(V) oxo salophen from a manganese(III) perbenzoate. The O−O bond heterolysis reaction that produces the oxo is not facilitated by intramolecular proton transfer from the acid hanging group of the HSX platform. Instead, the hanging group stabilizes the catalyst against oxidative degradation and, consistent with recent predictions of theory, is geometrically matched to promote the end-on coordination of a H₂O₂ substrate prior to its oxidation at the manganese(V) oxo center.

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