Chemically Rational Modification of Integrated Cubane-type Frameworks

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The exploitation of the reaction of the triple cubane-type cluster 1 with MeOH was undertaken to understand the heterogeneous MeOH/MoO_3 catalytic system. We found novel conversion, outlined in Scheme, of cluster 1 to trishomocubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](2) then to a linear quadruple cubane-type cluster [(RhCp*)_2Mo_3O_9(OMe)_4](3).The molecular structure of clusters 2 and 3 were established by single crystal X-ray analyses and characterized by IR and NMR (^1H, and ^<13>C) spectroscopy. In cluster 2 the overall conformation of methoxy and Mo=O groups gives possible model for proton and non-redox methyl transfers involved in the MeOH/MoO_3 system, and cluster 3 is a congruent representation of the layer structure of MoO_3 recovered in the catalytic cycle of partial oxidation of MeOH. The clusters described here provide a novel synthetic example of extending topological equivalent of a recognizable unit in the infinite lattice.