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H2-Initiated Reversible Switching between Two-Dimensional Metallacycles and Three-Dimensional Cylinders

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Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, 220 Handan Road, 200433 Shanghai, People’s Republic of China
*E-mail for Y.-F.H.: [email protected]
*E-mail for G.-X.J.: [email protected]
Cite this: J. Am. Chem. Soc. 2014, 136, 41, 14608–14615
Publication Date (Web):September 12, 2014
Copyright © 2014 American Chemical Society

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    Although reversible covalent activation of molecular hydrogen (H2) by transition-metal complexes is a common reaction, H2-mediated sophisticated reversible arrangements of organometallic frameworks have not yet been described. Herein, we report unusual organometallic transformations in solution that can be accomplished by uptake or release of H2. An efficient route for synthesizing air- and moisture-stable 16-electron M2L2-type metallacycles under very mild conditions has been developed. The new organometallic metallacycles favor the binding of small ligands such as MeCN, Cl, CO, and pyridine. The reaction of a coordinatively unsaturated 16-electron M2L2-type macrocyclic complex featuring thione ligands with 1 atm of H2 leads to the isolation of a 18-electron M2L3-type cylinder, along with hydride species. Remarkably, the obtained mixture underwent loss of H2 in a facile manner upon heating to re-form the starting M2L2-type complex. A possible mechanism is proposed for the reversible transformations.

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    Text, figures, tables, and CIF files giving synthesis and characterization details of thione ligands L1L7, structures of 9(OTf) and L2, bond distances and angles and crystal data and structure refinement details for all compounds, and X-ray crystallographic data for L2, 1a(OTf)4, 1a(NO3)4, 1a(BF4)4, 1b(OTf)4, 3(OTf)4, 5(OTf)4, 6(OTf)4, 7(OTf)4, 8(OTf)4, 8(NO3)4, 9(OTf), 10(OTf)4, 12(OTf)4, [2(Py)2](OTf)4, and [2(Cl)2](OTf)2. This material is available free of charge via the Internet at

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