Activation of a water molecule using a mononuclear Mn complex: from Mn-aquo, to Mn-hydroxo, to Mn-oxyl via charge compensation

被引：46

作者：

Lassalle-Kaiser, Benedikt ^{[1
,6
]}

Hureau, Christelle ^{[2
,3
]}

Pantazis, Dimitrios A. ^{[4
,5
]}

Pushkar, Yulia ^{[6
]}

Guillot, Regis ^{[1
]}

Yachandra, Vittal K. ^{[6
]}

Yano, Junko ^{[6
]}

Neese, Frank ^{[4
,5
]}

Anxolabehere-Mallart, Elodie ^{[1
]}

机构：

[1] Univ Paris 11, ICMMO, CNRS, UMR 8182, F-91405 Orsay, France

[2] CNRS, LCC, F-31077 Toulouse, France

[3] Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France

[4] Univ Bonn, Inst Phys & Theoret Chem, D-53115 Bonn, Germany

[5] Max Planck Inst Bioinorgan Chem, D-45470 Mulheim, Germany

[6] Univ Calif Berkeley, Lawrence Berkeley Lab, Phys Biosci Div, Berkeley, CA 94720 USA

来源：

ENERGY & ENVIRONMENTAL SCIENCE | 2010年 / 3卷 / 07期

关键词：

OXYGEN-EVOLVING COMPLEX; RAY-ABSORPTION SPECTROSCOPY; COUPLED ELECTRON-TRANSFER; O BOND FORMATION; DENSITY-FUNCTIONAL THEORY; SCHIFF-BASE COMPLEXES; PHOTOSYNTHETIC MN4CA CLUSTER; UNSUPPORTED OXO BRIDGE; C-H OXIDATION; PHOTOSYSTEM-II;

D O I：

10.1039/b926990h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Activation of a water molecule by the electrochemical oxidation of a Mn-aquo complex accompanied by the loss of protons is reported. The sequential (2 x 1 electron/1 proton) and direct (2 electron/2 proton) proton-coupled electrochemical oxidation of a non-porphyrinic six-coordinated Mn(II)OH(2) complex into a mononuclear Mn(O) complex is described. The intermediate Mn(III)OH(2) and Mn(III) OH complexes are electrochemically prepared and analysed. Complete deprotonation of the coordinated water molecule in the Mn(O) complex is confirmed by electrochemical data while the analysis of EXAFS data reveals a gradual shortening of an Mn-O bond upon oxidation from Mn(II)OH(2) to Mn(III) OH and Mn(O). Reactivity experiments, DFT calculations and XANES pre-edge features provide strong evidence that the bonding in Mn(O) is best characterized by a Mn(III)-oxyl description. Such oxyl species could play a crucial role in natural and artificial water splitting reactions. We provide here a synthetic example for such species, obtained by electrochemical activation of a water ligand.

引用

页码：924 / 938

页数：15

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