High‐Spin and Reactive Fe₁₃ Cluster with Exposed Metal Sites

Abstract

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12, displaying a Fe13 core with M‐M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S = 13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core

“…Ed. [ 49 ] after the manuscript had been submitted. Our synthesis approach differs significantly from theirs in both the starting materials and the strategy of cluster assembly, indicating that an Fe 13 cluster can be synthesized through different approaches.…”

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

“…[10][11][12] APNCs capture the essential features of bulk metal chalcogenide catalysts including their highly delocalized electronic structures and flexible configuration of multimetallic sulfide active sites, both of which contribute to lowering activation energy barriers through cooperative multimetallic pathways. [13][14][15][16][17][18][19][20][21][22][23][24][25] Additionally, their discrete, atomically precise structures confer some distinct advantages. First, APNCs feature a well-defined arrangement of surface ligands that can be tuned to manipulate active site steric environment and electronic character.…”

Magnetic Metal Clusters and Superatoms

“…It is noteworthy that a single electron difference brings significant reconstruction of the spin electrons and even geometry in a magnetic metal cluster, including some metal oxide clusters. − In addition to the gas-phase preparation, reasonable research interest has also been attracted by using wet chemistry synthesis. Recently a ligand-protected Tp* 4 W 4 Fe 13 S 12 nanocluster has been synthesized (Figure c), shedding light on the enhanced stability of the metallic Fe 13 core . With a high magnetic moment ( S = 13) at room temperature, this cluster was demonstrated to bear potential application for magnetic materials.…”

“…Recently a ligand-protected Tp* 4 W 4 Fe 13 S 12 nanocluster has been synthesized (Figure 3c), shedding light on the enhanced stability of the metallic Fe 13 core. 22 With a high magnetic moment (S = 13) at room temperature, this cluster was demonstrated to bear potential application for magnetic materials.…”