Metal Cluster Catalysis

Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst

“…24−28 However, the elucidation of catalytic intermediates remains challenging across these platforms and relies heavily on computational modeling as opposed to direct experimental observation. 29 Combining molecular precision and scalability with catalytic competence, we introduced a family of molecular clusters M 3 Co 6 Se 8 L 6 (M = Fe, Co, Zn, Sn; L = Ph 2 PNTol − ) that incorporate three chemically addressable edge sites (M) on the surface of a Co/Se cluster core. 31−35 This synthetic construct is reminiscent of a broad class of catalytically active edge-doped transition metal dichalcogenide nanomaterials (Figure 1).…”

“…A large library of molecular ligand-stabilized transition metal nanoclusters exists, which are solution processable and have discrete chemical compositions. − Although the vast majority are not catalytically competent, some shed light on the physicochemical processes that underpin the catalytic interface between active site and multimetallic support. Select examples that provide these fundamental insights include clusters with inorganic [Fe 4 (μ 4 -O)], [RuCo 3 (μ 3 -O) 4 ], and [Fe 4 (μ 3 -S) 4 ] cores, wherein metal-bound oxo and imido substituents are stabilized by coordinative and electronic participation of a polymetallic support, and a series of trinuclear [Fe 3 ] and [Cr 3 ] clusters in which electronic coupling between the metal centers facilitates cooperative, multisite reactivity. , Catalytically active chalcogenide clusters are scarce, including [Mo 3 S 13 ] 2– and [MoFe 3 (μ 3 -S) 4 ], for hydrogen evolution and hydrazine reduction, , respectively, whereas metallic or metal oxide molecular clusters have been shown to catalyze a wider range of reactions. − However, the elucidation of catalytic intermediates remains challenging across these platforms and relies heavily on computational modeling as opposed to direct experimental observation. , …”

Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst

“…27,28 However, in part due to scalability challenges, the elucidation of catalytic intermediates remains challenging and relies heavily on computational modeling. 29,30 Our group introduced a family of molecular clusters, M3 (M3Co6Se8L6; M = Fe, Co, Zn, Sn; L = Ph2PNTol -), 16,[31][32][33][34] that incorporate three chemically addressable edge sites (M) on the surface of a Co/Se cluster core, a construct reminiscent of edgedoped transition metal dichalcogenide nanoflakes (Figure 1). 6,7,11 Hemilabile edge-support interactions stabilize the three edge sites in protected low-coordinate states, 31 positioning them to function as catalytically active sites and enabling the systematic study of electronic metal-support interactions, 35 as well as allosteric 34 and multi-site dynamics on the cluster surface.…”

Suzuki–Miyaura Cross-Coupling Reaction Catalyzed by Al12M (M = Be, Al, C, and P) Superatoms with Different Numbers of Valence Electrons

“…Thus, clusters are expected to be potential catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. 10 For example, Corma and coworkers 11 reported that small gold clusters (3−10 atoms) formed by conventional gold salts and gold complexes could catalyze various organic reactions at room temperature, which clearly demonstrates the potential of small metal clusters as highly active catalysts for organic synthesis. Subsequently, they found that Pd 3 and Pd 4 clusters generated by the interaction of palladium nanoparticles with aqueous solvents were highly active species in catalyzing the SM reaction, whereas neither mononuclear palladium complexes nor palladium nanoparticles were active species.…”