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

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.