期刊
INORGANIC CHEMISTRY
卷 48, 期 21, 页码 10024-10035出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic9006668
关键词
-
资金
- University of California, Berkeley
- Dreyfus, Beckman, Packard
- Sloan Foundations
- LBNL Chemical Sciences Division [403801]
- LBNL/DOE Helios SERC [51HEI12B]
- National Institutes of Health [1S10RR02239301]
We report a hydrogen-bond functionalized N4Py ligand platform (N, N-bis(2-R-6-pyridylmethyl)-N-bis(2-pyridyl)methylamine; R = neopentyl-NH, N4py2(NpNH), g; R = phenyl-NH, N4Py(2PhNH), 10) and the ability of its iron(II)-triflate [(N4PyFeII)-Fe-2R(OTf)][OTf] complexes (R = NpNH, 11; R = PhNH, 12) to activate and reduce dioxygen in a synthetic cycle by coupled proton and electron transfer. A pair of iron(III)-hydroxide [N4Py(2R)Fe(III)(OH)][OTf](2) complexes (R = NpNH, 13; R = PhNH, 14) are isolated and structurally and spectroscopically characterized after exposure of the iron(II)-triflate precursors to 1 atm of O-2 at ambient temperature. The stability of this system to acids and bases allows regeneration of the labile iron(II)-triflate starting materials by sequential electron and proton transfer with cobaltocene and triflic acid, respectively, or through direct proton-coupled reduction with ascorbic acid. In the stepwise process, reduction of the iron(III)-hydroxide complexes with cobaltocene gives structurally homologous iron(II)-hydroxide [N4Py(2R)Fe(II)(OH)][OTf] congeners (R = NpNH, 15; R = PhNH, 16) that can be prepared independently from 11 and 12 with 20% aq. NaOH. Additions of triflic acid to complexes 15 and 16 furnish the starting compounds 11 and 12, respectively, to complete the synthetic cycle. The combined data establish a synthetic cycle for O-2 reduction by an iron platform that manages proton and electron transfer through its first and second coordination spheres.
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