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


ABSTRACT: A Mn(iv) complex featuring a terminal oxo ligand, [MnIV(O)(ditox)3][K(15-C-5)2] (3; ditox = t Bu2MeCO-, 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.

SUBMITTER: Halbach RL 

PROVIDER: S-EPMC5958342 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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

Halbach Robert L RL   Gygi David D   Bloch Eric D ED   Anderson Bryce L BL   Nocera Daniel G DG  

Chemical science 20180426 19


A Mn(iv) complex featuring a terminal oxo ligand, [Mn<sup>IV</sup>(O)(ditox)<sub>3</sub>][K(15-C-5)<sub>2</sub>] (<b>3</b>; ditox = <sup><i>t</i></sup> Bu<sub>2</sub>MeCO<sup>-</sup>, 15-C-5 = 15-crown-5-ether) has been isolated and structurally characterized. Treatment of the colorless precursor [Mn<sup>II</sup>(ditox)<sub>3</sub>][K(15-C-5)<sub>2</sub>] (<b>2</b>) with iodosobenzene affords <b>3</b> as a green free-flowing powder in high yields. The X-ray crystal structure of <b>3</b> reveals  ...[more]

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