Multistep Cascade Catalytic Reactions Employing Bifunctional Framework Compounds.

Multistep cascade reactions are important to achieve atom as well as step economy over conventional synthesis. This approach, however, is limited due to the incompatibility of the available reactive centers in a catalyst. In the present study, new MOF compounds, [Zn2(SDBA)(3-ATZ)2]·solvent, I and II, with tetrahedral Zn centers as good Lewis acidic sites and the free amino group of the 3-amino triazole ligand as a strong Lewis base center were shown to perform 4-step cascade/tandem reaction in a facile manner. Effective conversion of benzaldehyde dimethyl acetal in the presence of excess nitromethane at 100 °C in water to 1-(1,3-dinitropropan-2-yl) benzene was achieved in 10 h with yields of ∼95% (I) and ∼94% (II). This 4-step cascade reaction proceeds via deacetalization (Lewis acid), Henry (Lewis base), and Michael (Lewis base) reactions. The present work highlights the importance of spatially separated functional groups in multistep tandem catalysis─the examples of which are not common.

Selective Separation of Aliphatic Nitriles by Employing a Two-Dimensional Interdigitated Coordination Polymer.

A room-temperature slow diffusion reaction of the metal nitrates [M=ZnII and CoII ] with 5-azido isophthalic acid (AIPA) and 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (BPDB) resulted in a new two-dimensional interdigitated coordination polymer, [M(C8 H3 N3 O4 )(C12 H10 N4 )]⋅DMF [DMF=dimethyl formamide (C3 H7 NO)]. The non-bonded DMF molecules were found to exchange through a single-crystal to single-crystal (SCSC) fashion with many aliphatic nitrile compounds. More importantly, the present compound, I⋅DMF(Zn) appears to absorb cis-crotononitrile selectively from the cis/trans mixture as well as a mixture containing the structural isomer (allylnitrile). It also preferentially absorbs propionitrile from an equimolar mixture of acetonitrile, propionitrile, and butyronitrile (1:2:1). The cobalt compound exhibits anti-ferromagnetic behavior.

Stabilization of Cu7 clusters in azide networks: syntheses, structures and magnetic behaviour.

Two new azide bridged copper(II) coordination polymer compounds, [Cu7(N3)14(C3H10N2)(C4H13N3)]n (I) and [Cu7(N3)14(C3H10N2)(C5H15N3)2]n (II) [where C3H10N2 = 1,2-diaminopropane (1,2-DAP); C4H13N3 = diethylenetriamine (DETA); C5H15N3 = N-2-aminoethyl-1,3-propanediamine (AEDAP)] were prepared by employing a room temperature diffusion technique involving three layers. Single crystal studies reveal that both compounds I and II, have similar connectivity forming Cu7 clusters through end-on (EO) bonding of the azide. The Cu7 clusters are connected through end-to-end (EE) connectivity of the azides forming three-dimensional structures. Magnetic studies confirmed the ferromagnetic interactions within the Cu7 units and revealed the occurrence of concomitant ferro- and antiferro-magnetic interactions between these clusters. As a result I behaves as a weak-ferromagnet with TC = 10 K.