期刊
ENERGY & ENVIRONMENTAL SCIENCE
卷 3, 期 7, 页码 924-938出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/b926990h
关键词
-
资金
- DOE
- Office of Science, Office of Basic Energy Sciences (OBES), Chemical Sciences, Geosciences, and Biosciences Division [DE-AC02-05CH11231]
- NIH [GM 55302]
- France-Berkeley Fund
- OBER
- NIH, NCRR
- European Project [SolarH2]
- ANR
- Max-Plank society
- University of Bonn
- Special Research Unit [SFB 813]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R56GM055302, R01GM055302] Funding Source: NIH RePORTER
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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据