The CoMo hollow bimetallic oxide has been exploited in the aerobic epoxidation of cyclohexene containing labile allylic hydrogen atoms using ethylbenzene as a solvent. Cooperativity between Co(II) and Mo(VI) sites consisting of Co-O-Mo or Mo-O delta- ...Co delta+ unit on hollow oxide surfaces is investigated for controlling preferred epoxidation catalysis via tandem oxygen transfer. Various characterization techniques like XRD diffraction, N-2 physisorption, TEM, and Raman, XPS, Infrared, and UV-vis spectroscopies are employed to reveal the relationship between structure of active sites and catalytic performance. Together with these comprehensive experimental and computational studies, in this unique tandem catalytic process, Co(II) sites effectively mediate the first step of the overall oxidation cycle yielding a phenylethylperoxy radical by oxygen activation [Co(II) to Co(III) -O-2(-) to phenylethyl radical and finally to a phenylethylperoxy radical]. On the other hand, Mo(VI) sites are shown to be the excellent catalytic species for the subsequent epoxidation step by the transfer of oxygen atom of the phenylethylperoxy radical to cyclohexene. Hence, a 59% epoxidation selectivity with 33% cyclohexene conversion is accomplished through the required combination of Co(II) and Mo(VI) (2:1), allowing to tune epoxidation efficiency toward higher driving forces (relative to oxygenation of allylic hydrogen atom). This remarkably different catalytic performances between Co(II) and Mo(VI) can be attributed to the stronger overall polarization ability of Mo(VI) toward sigma(star) O-O orbital of the O-O unit derived from its d-type orbitals, which helps the donor -acceptor interactions with the double bond.
