Chemically Rational Modification of Integrated Cubane-type Frameworks

探索了三方烷型簇合物1与甲醇的反应，以了解甲醇/MoO_3多相催化体系。我们发现了一种新的转变，即簇1转变为三聚立方烷型簇合物[(rhcp*)_2Mo_3O_9(Ome)_4](2)，然后转变为线性四方烷型簇合物[(rhcp*)_2Mo_3O_9(Ome)_4](3)。通过单晶X-射线分析确定了簇合物2和3的分子结构，并用红外光谱和核磁共振谱(^1H和^&lt；13&gt；C)进行了表征。在簇2中，甲氧基和Mo=O基团的整体构象给出了甲醇/MoO_3体系中质子和非氧化还原甲基转移的可能模型，簇3是MeOH部分氧化催化循环中回收的MoO_3层结构的同质表示。这里描述的簇提供了在无限格子中扩展可识别单元的拓扑等价的一个新的合成例子。

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.