title: Photoreduction of carbon dioxide to carbon monoxide with hydrogen catalyzed by a rhenium(I) phenanthroline-polyoxometalate hybrid complex.
abstract: 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)CH(3)CN-MHPW(12)O(40) (L = 15-crown-5-phenanthroline, M = Na(+), H(3)O(+)). X-ray diffraction, (1)H and (13)C 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)CH(3)CN-MHPW(12)O(40) can oxidize H(2) to two protons and two electrons which in the presence of visible light can catalyze the photoreduction of CO(2) 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 PW(V)W(VI)(11)O(40) and a Re(0) species with a tentative assignment of the intermediate as Re(0)(L)(CO)(3)(S)-MH(3)PW(V)W(VI)(11)O(40).
authors.affiliation: Department of Organic Chemistry and, Chemical Research Support Unit, Weizmann Institute of Science, Rehovot, Israel 76100.
authors.forename: Jessica
authors.initials: J
authors.lastname: Ettedgui
authors.forename: Yael
authors.initials: Y
authors.lastname: Diskin-Posner
authors.forename: Lev
authors.initials: L
authors.lastname: Weiner
authors.forename: Ronny
authors.initials: R
authors.lastname: Neumann
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002248:Carbon Monoxide / Q000138:chemical synthesis* / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry; D055668:Photochemical Processes; D012211:Rhenium / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry; D000099294:Polyoxometalates
chemical_list: D002245:Carbon Dioxide; D002248:Carbon Monoxide; D006859:Hydrogen; D009942:Organometallic Compounds; D010618:Phenanthrolines; D012211:Rhenium; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates