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Issue 19, 2018
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Structurally characterized terminal manganese(IV) oxo tris(alkoxide) complex

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Abstract

A Mn(IV) complex featuring a terminal oxo ligand, [MnIV(O)(ditox)3][K(15-C-5)2] (3; ditox = tBu2MeCO, 15-C-5 = 15-crown-5-ether) has been isolated and structurally characterized. Treatment of the colorless precursor [MnII(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–Oterm = 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 [MnIV(O)(ditox)3] furnishes a model for the proposed terminal oxo of the unique manganese of the oxygen evolving complex of photosystem II.

Graphical abstract: Structurally characterized terminal manganese(iv) oxo tris(alkoxide) complex

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Publication details

The article was received on 12 Mar 2018, accepted on 16 Apr 2018 and first published on 26 Apr 2018


Article type: Edge Article
DOI: 10.1039/C8SC01164H
Citation: Chem. Sci., 2018,9, 4524-4528
  • Open access: Creative Commons BY license
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    Structurally characterized terminal manganese(IV) oxo tris(alkoxide) complex

    R. L. Halbach, D. Gygi, E. D. Bloch, B. L. Anderson and D. G. Nocera, Chem. Sci., 2018, 9, 4524
    DOI: 10.1039/C8SC01164H

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