Influence of a "Dangling" Co(II) Ion Bound to a [MnCo3 O4 ] Oxo Cubane

Journal of the American Chemical Society
Andy I NguyenT Don Tilley

Abstract

Cobalt(II), in the presence of acetate and nitrate, quantitatively adds to the manganese-cobalt oxido cubane MnIVCoIII3O4(OAc)5(py)3 (1) to furnish the pentametallic dangler complex MnIVCoIII3CoIIO4(OAc)6(NO3)(py)3 (2). Complex 2 is structurally reminiscent of photosystem II's oxygen-evolving center, and is a rare example of a transition-metal "dangler" complex. Superconducting quantum interference device magnetometry and density functional theory calculations characterize 2 as having an S = 0 ground state arising from antiferromagnetic coupling between the CoII and MnIV ions. At higher temperatures, an uncoupled state dominates. The voltammogram of 2 has four electrochemical events, two more than that of its parent cubane 1, suggesting that addition of the dangler increases available redox states. Structural, electrochemical, and magnetic comparisons of complexes 1 and 2 allow a better understanding of the dangler's influence on a cubane.

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Citations

Jul 16, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Oleh StetsiukNarcis Avarvari
Apr 29, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Ritwik ModakSanchita Goswami
Nov 26, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Jonathan A KephartAlexandra Velian
May 24, 2019·Journal of the American Chemical Society·Fangyuan SongGreta R Patzke
Jan 22, 2022·Journal of the American Chemical Society·Jaruwan AmtawongT Don Tilley

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