Neal P. Mankad

The Role of Terminal Heavy Chalcogenide Ligands in Enabling Hydride Transfer Reactivity of W═E (E = S, Se) Models for Molybdenum Hydroxylases

Ananthu V. Modappilappally, Neal P. Mankad

Whereas molybdenum-dependent hydroxylases in the xanthine oxidase family catalyze site-selective C-H hydroxylation reactions using terminal molybdenum sulfide (Mo═S) active sites, certain variants such as nicotinate dehydrogenase (NDH) replace the sulfide ligand by a selenide (Mo═Se) to enable activation of less reactive C-H …

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The role of terminal heavy chalcogenide ligands in enabling hydride transfer reactivity of W=E (E = S, Se) models for molybdenum hydroxylases

Ananthu V. Modappilappally, Neal P. Mankad

Whereas molybdenum-dependent hydroxylases in the xanthine oxidase family catalyze site-selective C–H hydroxylation reactions utilizing terminal molybdenum sulfide (Mo=S) active sites, certain variants such as nicotinate dehydrogenase (NDH) replace the sulfide ligand by a selenide (Mo=Se) to enable activation of less reactive C–H …

A Synthetic Molybdenum Hydroxylase Compound That Cleaves C–H Bonds by Hydride Abstraction

Ananthu V. Modappilappally, Neal P. Mankad

abstraction paradigm for C-H activation and charts the reaction pathways needed for catalytic turnover.

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Noninnocent Cyclopentadienyl Reactivity in an Al/Cr Heterobimetallic Complex

Roushan Prakash Singh, Neal P. Mankad

The cyclopentadienyl (Cp) ligand plays a pivotal role in organometallic chemistry. While it is traditionally regarded as an ancillary spectator ligand, increasing evidence shows that Cp and Cp* ligands can actively engage in bond-forming reactions with nucleophiles, electrophiles, and radicals to afford …

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A Synthetic Molybdenum Complex that Mimics All Four Molybdopterin Enzyme Families and Enables Catalytic C–H Oxidation

Prajal Chhetri, Ananthu V. Modappilappally, Xin Zheng, Neal P. Mankad

Molybdopterin enzymes catalyze a remarkably diverse array of redox transformations, ranging from oxyanion reduction to C–H hydroxylation, through MoVI/MoIV cycling at active sites with conserved dithiolate-coordinated structures. Synthetic models of these active sites have historically struggled to replicate this chemical versatility in …

A synthetic molybdenum hydroxylase compound that cleaves C-H bonds by hydride abstraction

Ananthu V Modappilappally, Neal P. Mankad

Molybdenum-dependent hydroxylases catalyze site-selective C-H hydroxylation reactions involving hydride abstraction pathways, yet no synthetic system has previously reproduced this reactivity. Here we report a synthetic molybdenum hydroxylase that achieves C-H bond cleavage and hydroxylation through a bio-inspired H⁻ abstraction pathway. A cis …

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Tandem Electrocatalysis: Cathodic Epoxidation of Alkenes by a Manganese Salophen Catalyst

Nadira Parvin Lata, Ritabrata Mondal, Xin Zheng, Neal P. Mankad et autres

Electrocatalytic oxygen-atom transfer (eOAT) driven by the oxygen reduction reaction (ORR) offers a direct route to couple O 2 activation with the synthesis of oxygenated products. Although homogeneous Mn-based complexes have shown promise as ORR and eOAT catalysts separately, the factors that …

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Electrocatalytic Oxygen Atom Transfer by a Manganese Based Complex

Nadira Parvin Lata, Shivam Singh, Neal P. Mankad, Ksenija D. Glusac

The development of environmentally benign oxidation methods is a critical goal in sustainable chemistry. Oxygen atom transfer (OAT) reactions, which utilize molecular oxygen (O₂) as the terminal oxidant, offer a direct and atom-economical route to functionalize organic substrates. However, selective reduction of …

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Heterobinuclear Molecular Precursors Direct the Formation of Supported Subnanometer Cu–M Clusters with Tunable Catalytic Behavior

Mazal Kostan-Carmiel, Hadar Shema, Hsien‐Cheng Yu, Griffin A. Canning et autres

Subnanometer bimetallic clusters hold great promise for catalytic applications due to their unique electronic properties and high surface-to-volume ratios. However, precise control over their composition and size remains a major challenge, particularly for immiscible metal pairs. Here, we report a surface-anchored molecular …

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CpFe(CO)2 Radical Generated from Dinuclear [CpFe(CO)2]2 and Mononuclear (Cp)(CO)2Fe(H): Density Functional Theory Is Accurate for One, But Not Both

Kevin P. Quirion, Roushan Prakash Singh, Neal P. Mankad, Daniel H. Ess

Density functional theory (DFT) methods remain the most practical approach to calculating properties and reaction mechanisms of transition metal complexes. While the accuracy of DFT methods has been evaluated for some properties of mononuclear organometallic complexes there has been a general lack …

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Chlorination and oxygenation of carbon electrodes for covalent attachment of thiol-terminated molecules

Xin Zheng, Igor L. Bolotin, Beria Tanriover, Rathnayake Mudiyanselage Kumuditha Anjala Rathnayake et autres

This study reports covalent edge plane chlorination of carbon electrodes and their subsequent functionalization with thiol-containing redox-active molecules. Specifically, the reactivity of edge C-H groups on glassy carbon (GC) and carbon powder (CP) electrodes with chlorinating reagents, iodine monochloride and iron(III) chloride, …

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Dimolybdenum Paddlewheel Complexes with Cation Binding Sites as Electrolyte Additives to Manipulate the Solid-Electrolyte Interphase at Lithium Metal Anodes

Simon G. Gersib, Erik J. Askins, Matthew Li, S. M. Supundrika Subasinghe et autres

induces immobilization of cationically charged aggregates (or products thereof) into the solid electrolyte interphase (SEI), imparting multiple beneficial functions. The modified SEI was found to protect the LMA against parasitic side reactions, produce modest but measurable improvements to Li plating properties (e.g., …

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