Ligand exchanges and selective catalytic hydrogenation in molecular single crystals

摘要

Chemical reactions inside single crystals are likely to be highly selective, but examples of single crystal to single crystal (SC-SC) transformations are uncommon, because crystallinity is difficult to retain following the rearrangement of atoms in the solid state. The most widely studied SC-SC transformations involve solvent exchange reactions in porous coordination polymers or metal-organic frameworks, which take advantage of the robust polymeric networks of the hosts. Examples of reactions occurring within molecular organic crystals generally involve photo-induced reactions, such as the coupling of alkenes or alkynes within the crystal. For nonporous molecular inorganic or organometallic crystals, single-crystal transformations involving the formation or cleavage of metal-ligand bonds are rare; known examples usually involve ligand loss from the single crystal and reversible religation, a process sometimes accompanied by decay of the single crystal to a microcrystalline powder. Here we report a series of SC-SC transformations that involve the interchange of multiple small gaseous ligands (N_2, CO, NH_3, C_2H_4) H_2 and O_2) at an iridium centre in molecular single crystals of a pincer Ir(I) complex. The single crystal remains intact during these ligand-exchange reactions, which occur within the crystal and do not require prior ligand extrusion. We reveal a selective catalytic transformation within a nonporous molecular crystal: pincer iridium single crystals ligated with nitrogen, ethyl-ene or hydrogen show selective hydrogenation of ethylene relative to propylene (25:1) when surface sites are passified by CO.