Selective Cobalt-Mediated Formation of Hydrogen Peroxide from Water under Mild Conditions via Ligand Redox Non-Innocence.

Despite the broad importance of hydrogen peroxide (H2O2) in oxidative transformations, there are comparatively few viable routes for its production. The majority of commercial H2O2 is currently produced by the stepwise reduction of dioxygen (O2) via the anthraquinone process, but direct electrochemical formation from water (H2O) would have several advantages─namely, avoiding flammable gases or stepwise separations. However, the selective oxidation of H2O to form H2O2 over the thermodynamically favored product of O2 is a difficult synthetic challenge. Here, we present a molecular H2O oxidation system with excellent selectivity for H2O2 that functions both stoichiometrically and catalytically. We observe high efficiency for electrocatalytic H2O2 production at low overpotential with no O2 observed under any conditions. Mechanistic studies with both calculations and kinetic analyses from isolated intermediates suggest that H2O2 formation occurs in a bimolecular fashion via a dinuclear H2O2-bridged intermediate with an important role for a redox non-innocent ligand. This system showcases the ability of metal-ligand cooperativity and strategic design of the secondary coordination sphere to promote kinetically and thermodynamically challenging selectivity in oxidative catalysis.

Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons.

Alkyne semihydrogenation is a broadly important transformation in chemical synthesis. Here, we introduce an electrochemical method for the selective semihydrogenation of terminal alkynes using a dihydrazonopyrrole Ni complex capable of storing an H2 equivalent (2H+ + 2e-) on the ligand backbone. This method is chemoselective for the semihydrogenation of terminal alkynes over internal alkynes or alkenes. Mechanistic studies reveal that the transformation is concerted and Z-selective. Calculations support a ligand-based hydrogen-atom transfer pathway instead of a hydride mechanism, which is commonly invoked for transition metal hydrogenation catalysts. The synthesis of the proposed intermediates demonstrates that the catalytic mechanism proceeds through a reduced formal Ni(I) species. The high yields for terminal alkene products without over-reduction or oligomerization are among the best reported for any homogeneous catalyst. Furthermore, the metal-ligand cooperative hydrogen transfer enabled with this system directs the efficient flow of H atom equivalents toward alkyne reduction rather than hydrogen evolution, providing a blueprint for applying similar strategies toward a wide range of electroreductive transformations.

Isolation and Crystallographic Characterization of an Octavalent Co2O2 Diamond Core.

High-valent cobalt oxides play a pivotal role in alternative energy technology as catalysts for water splitting and as cathodes in lithium-ion batteries. Despite this importance, the properties governing the stability of high-valent cobalt oxides and specifically possible oxygen evolution pathways are not clear. One root of this limited understanding is the scarcity of high-valent Co(IV)-containing model complexes; there are no reports of stable, well-defined complexes with multiple Co(IV) centers. Here, an oxidatively robust fluorinated ligand scaffold enables the isolation and crystallographic characterization of a Co(IV)2-bis-µ-oxo complex. This complex is remarkably stable, in stark contrast with previously reported Co(IV)2 species that are highly reactive, which demonstrates that oxy-Co(IV)2 species are not necessarily unstable with respect to oxygen evolution. This example underscores a new design strategy for highly oxidizing transition-metal fragments and provides detailed data on a previously inaccessible chemical unit of relevance to O-O bond formation and oxygen evolution.

Aliovalent Substitution Tunes Physical Properties in a Conductive Bis(dithiolene) Two-Dimensional Metal-Organic Framework.

Two-dimensional conductive metal-organic frameworks have emerged as promising electronic materials for applications in (opto)electronic, thermoelectric, magnetic, electrocatalytic, and energy storage devices. Many bottom-up or postsynthetic protocols have been developed to isolate these materials or further modulate their electronic properties. However, some methodologies commonly used in classic semiconductors, notably, aliovalent substitution, are conspicuously absent. Here, we demonstrate how aliovalent Fe(III) to Ni(II) substitution enables the isolation of a Ni bis(dithiolene) material from a previously reported Fe analogue. Detailed characterization supports the idea that aliovalent substitution of Fe(III) to Ni(II) results in an in situ oxidation of the organic dithiolene linker. This substitution-induced redox tuning modulates the electronic properties in the system, leading to higher electrical conductivity and Hall mobility but slightly lower carrier densities and weaker antiferromagnetic interactions. Moreover, this aliovalent substitution improves the material's electrochemical stability and thus enables pseudocapacitive behavior in the Ni material. These results demonstrate how classic aliovalent substitution strategies in semiconductors can also be leveraged in conductive MOFs and add further support to this class of compounds as emerging electronic materials.

Catalytic, Spectroscopic, and Theoretical Studies of Fe4S4-Based Coordination Polymers as Heterogenous Coupled Proton-Electron Transfer Mediators for Electrocatalysis.

Iron-sulfur clusters play essential roles in biological systems, and thus synthetic [Fe4S4] clusters have been an area of active research. Recent studies have demonstrated that soluble [Fe4S4] clusters can serve as net H atom transfer mediators, improving the activity and selectivity of a homogeneous Mn CO2 reduction catalyst. Here, we demonstrate that incorporating these [Fe4S4] clusters into a coordination polymer enables heterogeneous H atom transfer from an electrode surface to a Mn complex dissolved in solution. A previously reported solution-processable Fe4S4-based coordination polymer was successfully deposited on the surfaces of different electrodes. The coated electrodes serve as H atom transfer mediators to a soluble Mn CO2 reduction catalyst displaying good product selectivity for formic acid. Furthermore, these electrodes are recyclable with a minimal decrease in activity after multiple catalytic cycles. The heterogenization of the mediator also enables the characterization of solution-phase and electrode surface species separately. Surface enhanced infrared absorption spectroscopy (SEIRAS) reveals spectroscopic signatures for an in situ generated active Mn-H species, providing a more complete mechanistic picture for this system. The active species, reaction mechanism, and the protonation sites on the [Fe4S4] clusters were further confirmed by density functional theory calculations. The observed H atom transfer reactivity of these coordination polymer-coated electrodes motivates additional applications of this composite material in reductive H atom transfer electrocatalysis.

Variable Peripheral Ligand Donation Tunes Electronic Structure and NIR II Emission in Tetrathiafulvalene Tetrathiolate Diradicaloids.

Near-infrared (NIR) lumiphores are promising candidates for numerous imaging, communication, and sensing applications, but they typically require large, conjugated scaffolds to achieve emission in this low-energy region. Due to the extended conjugation and synthetic complexity required, it is extremely difficult to tune the photophysical properties of these systems for desired applications. Here, we report facile tuning of deep NIR-emitting diradicaloid complexes through simple modification of peripheral ligands. These new lumiphores are rare examples of air-, acid-, and water-stable emissive diradicaloids. We apply a simple Hammett parameter-based strategy to tune the electron donation of the capping ligand across a series of commercially available triarylphosphines. This minor peripheral modification significantly alters the electronic structure, and consequently, the electrochemical, photophysical, and magnetic properties of the tetrathiafulvalene tetrathiolate (TTFtt)-based lumiphores. The resultant ∼100 nm absorption and emission range spans common laser lines and the desirable telecom region (ca. 1260-1550 nm). Furthermore, these lumiphores are sensitive to local dielectrics, distinguishing them as promising candidates for ratiometric imaging and/or barcoding in the deep NIR region.

Metal-ligand cooperativity in chemical electrosynthesis.

Electrochemistry has been an increasingly useful tool for organic synthesis, as it can selectively generate reactive intermediates under mild conditions using an applied potential. Concurrently, synergistic activity of a metal and a ligand has been used in thermal catalysis and electrocatalytic renewable fuel generation for substrate selectivity and improved catalyst activity. Combining these synthetic strategies is an attractive approach for mild, selective, and sustainable electrosynthesis. This perspective discusses examples of metal-ligand synergistic catalysis in electrochemical applications in organic and organometallic synthesis. The range of reactions and ligand design principles illustrates many opportunities for further discovery in this area and the potential for far-reaching synthetic benefits.

Synthesis of a potassium capped terminal cobalt-oxido complex.

An unusual example of a potassium capped terminal cobalt-oxido complex has been isolated and crystallographically characterized. The synthesis of [tBu,TolDHP]CoOK proceeds from a previously reported parent compound, [tBu,TolDHP]CoOH, via deprotonation with KOtBu. Structural and electronic characterization suggest a weakly coupled dimer in a distinct seesaw geometry with a Co(III) oxidation state and a non-innocent radical ligand.