期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 2, 页码 188-190出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja1078199
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资金
- Divadol Foundation
- Israel Science Foundation
- Bernice and Peter Cohn Catalysis Research Fund
- Helen and Martin Kimmel Center for Molecular Design
A phenanthroline ligand decorated at the 5,6-position with a 15-crown-5 ether was used to prepare a metalorganic-polyoxometalate hybrid complex Re-I(L)(CO)(3)CH3CN-MHPW12O40 (L = 15-crown-5-phenanthroline, M = Na+, H3O+). X-ray diffraction, H-1 and C-13 NMR, ESI-MS, IR, and elemental analysis were used to characterize this complex. In the presence of Pt/C, the polyoxometalate moiety in Re-I(L)(CO)(3)CH3CN-MHPW12O40 can oxidize H-2 to two protons and two electrons which in the presence of visible light can catalyze the photoreduction of CO2 to CO with H-2 as the reducing agent instead of the universally used amines as sacrificial reducing agents. An EPR spectrum of a stable intermediate species under reaction conditions shows characteristics of a (PWW11O40)-W-V-O-VI and a Re-0 species with a tentative assignment of the intermediate as Re-0(L)(CO)(3)(S)-(MH3PWW11O40)-W-V-O-VI.
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