Issue 19, 2018

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


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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Article information

Article type
Edge Article
12 Mar 2018
16 Apr 2018
First published
26 Apr 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 4524-4528

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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