Structurally characterized terminal manganese(iv) oxo tris(alkoxide) complex

A Mn(iv) complex featuring a terminal oxo ligand, [Mn(IV)(O)(ditox)(3)][K(15-C-5)(2)] (3; ditox = (t)Bu(2)MeCO(–), 15-C-5 = 15-crown-5-ether) has been isolated and structurally characterized. Treatment of the colorless precursor [Mn(II)(ditox)(3)][K(15-C-5)(2)] (2) with iodosobenzene affords 3 as a...

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Detalles Bibliográficos
Autores principales: Halbach, Robert L., Gygi, David, Bloch, Eric D., Anderson, Bryce L., Nocera, Daniel G.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5958342/
https://www.ncbi.nlm.nih.gov/pubmed/29896395
http://dx.doi.org/10.1039/c8sc01164h
Descripción
Sumario:A Mn(iv) complex featuring a terminal oxo ligand, [Mn(IV)(O)(ditox)(3)][K(15-C-5)(2)] (3; ditox = (t)Bu(2)MeCO(–), 15-C-5 = 15-crown-5-ether) has been isolated and structurally characterized. Treatment of the colorless precursor [Mn(II)(ditox)(3)][K(15-C-5)(2)] (2) with iodosobenzene affords 3 as a green free-flowing powder in high yields. The X-ray crystal structure of 3 reveals a pseudotetrahedral geometry about the central Mn, which features a terminal oxo (d(Mn–O(term) = 1.628(2) Å)). EPR spectroscopy, SQUID magnetometry, and Evans method magnetic susceptibility indicate that 3 consists of a high-spin S = 3/2 Mn(iv) metal center. 3 promotes C–H bond activation by a hydrogen atom abstraction. The [Mn(IV)(O)(ditox)(3)](–) furnishes a model for the proposed terminal oxo of the unique manganese of the oxygen evolving complex of photosystem II.

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