Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO₃⁻Cluster Anions

Direct conversion of methane with carbon dioxide to value‐added chemicals is attractive but extremely challenging because of the thermodynamic stability and kinetic inertness of both molecules. Herein, the first dinuclear cluster species, RhVO 3 − , has been designed to mediate the co‐conversion of CH 4 and CO 2 to oxygenated products, CH 3 OH and CH 2 O, in the temperature range of 393–600 K. The resulting cluster ions RhVO 3 CO − after CH 3 OH formation can further desorb the [CO] unit to regenerate the RhVO 3 − cluster, leading to the successful establishment of a catalytic cycle for methanol production from CH 4 and CO 2 (CH 4 +CO 2 →CH 3 OH+CO). The exceptional activity of Rh‐V dinuclear oxide cluster (RhVO 3 − ) identified herein provides a new mechanism for co‐conversion of two very stable molecules CH 4 and CO 2 .