Photooxidation of hexacarbonylmolybdenum(0) in sodium zeolite Y to yield redox-interconvertible molybdenum(VI) oxide and molybdenum(IV) oxide monomers

An analysis of the photooxidation reaction of alpha-cage located, site II sodium cation anchored trans(ZONa)...(OC)Mo(CO)4(CO)...(NaOZ) exposed to O2 in sodium zeolite Y (Na56Y) has been carried out using various techniques (PXRD, EXAFS, MAS/DOR-NMR, EPR, XPS, UV-vis, FTIR, gravimetry). The results have shown that it cleanly and qunatitatively converts to molybdenum(VI) oxide and CO2 as the sole reaction products according to n[MO(CO)6]-Na56Y + 9/2nO2 -->(hnu) n[MoO3]-Na56Y + 6nCO2 over the full loading range 0 < n less-than-or-equal-to 16. Vacuum, thermally induced reductive elimination Of O2 from the molybdenum(VI) oxide photoproduct is quantitative at 400-degrees-C and yields molybdenum(IV) oxide with no evidence for any other products having oxygen stoichiometries differing from two and three. This reduction process can be quantitatively reversed by exposure of the molybdenum(IV) oxide product to O2 at 400-degrees-C, according to