Abstract
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 state1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19. 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 hosts2,8,9,10,11. Examples of reactions occurring within molecular organic crystals generally involve photo-induced reactions, such as the coupling of alkenes or alkynes within the crystal1,2,12,13,14,15. For nonporous molecular inorganic or organometallic crystals, single-crystal transformations involving the formation or cleavage of metal–ligand bonds are rare17,18,19,20,21; 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 powder20,21. Here we report a series of SC–SC transformations that involve the interchange of multiple small gaseous ligands (N2, CO, NH3, C2H4, H2 and O2) 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, ethylene or hydrogen show selective hydrogenation of ethylene relative to propylene (25:1) when surface sites are passified by CO.
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Acknowledgements
This work is financially supported by the National Science Foundation under the auspices of the Centre for Enabling New Technologies through Catalysis (CENTC).
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M.B. directed the project. Z.H. carried out all complex syntheses, crystallizations and reactions. P.S.W. carried out single crystal X-ray diffraction experiments and crystal structure determinations. M.B. and Z.H. analysed the data and wrote the manuscript.
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Supplementary crystallographic data for this paper has been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 728556 to 728561, 729323, 729324 and 759994 to 759996. These data can be obtained free of charge from http://www.ccdc.cam.ac.uk/data_request/cif.
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This file contains Supplementary Experiments, Methods and Synthesis, Supplementary Tables 1- 6, Supplementary Figures 1-7 with legends and References. (PDF 537 kb)
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Huang, Z., White, P. & Brookhart, M. Ligand exchanges and selective catalytic hydrogenation in molecular single crystals. Nature 465, 598–601 (2010). https://doi.org/10.1038/nature09085
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DOI: https://doi.org/10.1038/nature09085
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