Leveraging molecular metal–support interactions for H2 and N2 activation

Abstract

Many challenging chemical reactions require precious metal catalysts to proceed. Bio-inspired catalysts featuring multiple earth-abundant metals are an attractive alternative, as they offer boundless possibilities for facilitating processes that the constituent metals cannot mediate on their own. Our work utilizes a supporting metal as an electronic lever for tuning a base metal (Co, Ni) active site via a metal-metal bond. This approach has allowed for the development of metal-support catalysts for reductive N 2 silylation and olefin hydrogenation. The bimetallic catalysts display markedly enhanced activity compared to the analogous single metal centers. In this review, we investigate the role of the supporting metal in substrate binding, activation, and catalysis, to inform future efforts in the optimization and development of molecular metalsupport catalysts. Stoichiometric N−Si Bond Formation by an Iron Bimetallic Catalytic N−Si Bond Formation by Cobalt Bimetallics Mechanistic Investigation of N 2 Silylation Conclusions Highlights• The catalyst activity of a single metal was enhanced by a supporting metal.• Supporting metals were varied across the first-row period and down Group 13.• Metal-support bonding affects the metal's electronic state and ligand lability.• Group 13 supports induce H 2 binding at Ni and act cooperatively to cleave H 2 .• Transition metal supports promote N 2 binding and catalytic N 2 silylation at Co.

Tetranuclear Fe Clusters with a Varied Interstitial Ligand: Effects on the Structure, Redox Properties, and Nitric Oxide Activation

“…16 Analogous shifts in the distance between Fe and axial ligands trans to coordinated N 2 have been reported for monoiron models of nitrogenase. 17 …”

Cuprophilic Interactions in and between Molecular Entities

“…During the past few decades, studies on extended metal atomic chain (EMAC) or metal string complexesh ave increased due to their applications as supramolecular precursors and their potential to undergo multi-electron transfer processes, which are crucial for small molecule activation and catalysis. [80][81][82][83][84][85] In addition, EMAC complexes display interesting physical properties, such as electron-transfer processes in metal chainsa nd applications in molecular electronics. [86][87][88][89][90][91][92] Recent interesti nt he preparation of copper string complexes is due to their unique photoluminescence properties and potential applicationsi nm aterial science.…”

N2Reduction on Fe‐Based Complexes with Different Supporting Main‐Group Elements: Critical Roles of Anchor and Peripheral Ligands

“…The dominant contributions to the dative bond originate from the valence d‐shell of the active metal center and corresponding ligand‐centered bonding orbitals . In addition to main group donors, the Lewis acidic ancillary metals in bimetallic cobalt–dinitrogen complexes were also suggested to enhance the reverse‐dative bond flexibility and electronic tuning of the active metal, priming a positive effect on reactivity …”