Kinetic Versus Thermodynamic Metalation Enables Synthesis of Isostructural Homo- and Heterometallic Trinuclear Clusters
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abstract
Temperature-dependent metalation of the new hexadentate ligand (tris(5-(pyridin-2-yl)-1 H -pyrrol-2-yl)methane; H 3 TPM) enables the selective synthesis of both mononuclear ( i.e. Na(THF) 4 [Fe(TPM)], kinetic product) and trinuclear ( i.e. Fe 3 (TPM) 2 , thermodynamic product) complexes. Exposure of Na(THF) 4 [Fe(TPM)] to FeCl 2 or ZnCl 2 triggers cluster expansion to generate homo- or heterometallic trinuclear complexes, respectively. The developed approach enables systematic variation of ion content in isostructural metal clusters via programmed assembly.