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Dramatic influence of an anionic donor on the oxygen-atom transfer reactivity of an MnV–oxo complex

Neu, H., Quesne, Matthew, Yang, T., Prokop-Prigge, K. A., Lancaster, K. A., Donohoe, J., DeBeer, S., De visser, S. P. and Goldberg, D. P. 2014. Dramatic influence of an anionic donor on the oxygen-atom transfer reactivity of an MnV–oxo complex. Chemistry - a European Journal 20 (45) , pp. 14584-14588. 10.1002/chem.201404349

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Abstract

Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [MnV(O)(TBP8Cz)(CN)]− was generated from addition of Bu4N+CN− to the 5-coordinate MnV(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives Mn[BOND]O=1.53 Å, Mn[BOND]CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN− complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e−-reduced MnIII(CN)− complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol−1, ΔS≠=−10 cal mol−1 K−1. Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate MnV(O) complexes.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: WileyBlackwell
ISSN: 0947-6539
Last Modified: 25 Feb 2019 17:01
URI: http://orca-mwe.cf.ac.uk/id/eprint/88638

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