Transition metal catalysed homogeneous hydrogenation and dehydrogenation reactions for attaining plethora of organic scaffolds have evolved as a key domain of research in academia and industry. These protocols are atom-economic, greener, in line with the goal of sustainability, eventually pave the way for numerous novel environmentally benign methodologies. Appealing progress has been achieved in this realm of homogeneous catalysis utilizing noble metals. Owing to their high cost, less abundancy along with toxicity issues led the scientific community to search for sustainable alternatives. In this context, earth- abundant base metals have gained substantial attention culminating enormous progress in recent years, predominantly with pincer-type complexes of nickel, cobalt, iron, and manganese. In this regard, group VI chromium, molybdenum and tungsten complexes have been overlooked and remain underdeveloped despite their earth-abundancy and bio-compatibility. This review delineates a comprehensive overview in the arena of homogeneously catalysed (de)hydrogenation reactions using group VI base metals chromium, molybdenum, and tungsten till date. Various reactions have been described; hydrogenation, transfer hydrogenation, dehydrogenation, acceptorless dehydrogenative coupling, hydrogen auto transfer, along with their scope and brief mechanistic insights.

The rational design of activatable photosensitizers (aPSs) uncaged by specific disease biomarkers is currently booming due to their positive attributes to achieve targeted photodynamic therapy (PDT). In this context, we present here the synthesis and detailed photophysical characterization of a novel class of hetero-rosamine dyes bearing sulfur or selenium as bridging heavy atom and 4-pyridyl meso-substituent as optically tunable group. The main feature of such photoactive platforms is the spectacular change of their spectral properties depending on the caging/decaging status of their 4-pyridyl moiety (cationic pyridinium vs. neutral pyridine). The preparation of two alkaline phosphatase (ALP)-responsive probes (named Valkyrie probes) was achieved through formal N-quaternarization with 4-phosphoryloxybenzyl, the traditional recognition moiety for this important diagnostic enzyme. Bio-analytical validations including fluorescence/singlet oxygen phosphorescence enzyme assays and RP-HPLC-fluorescence/-MS analyses have enabled us to demonstrate the viability and effectiveness of this novel photosensitizer activation strategy. Since sulfur-containing Valkyrie probe also retains high fluorogenicity in the orange-red spectral range, this study highlights meso-pyridyl-substituted S-pyronin scaffolds as valuable candidates for the rapid construction of molecular phototheranostic platforms suitable for combined fluorescence diagnosis and PDT.

Acyl hydrazones are a class of synthetically important organic compounds that are recurrently in high demand for synthesis and use in various fields of chemistry and biology. We report the first Co(II) catalyzed one-component one-pot sustainable synthesis of acyl hydrazones only from acyl hydrazides under mild reaction conditions. Traditional and contemporary methodologies use two components (usually acyl hydrazides and aldehydes/ketones/alcohols/styrene) as the coupling partners. Our protocol, on the other hand, involves the in situ generation of aldehyde intermediate (detected by gas chromatography) from the acyl hydrazide, which then undergoes condensation with another molecule of the same acyl hydrazide in the same pot to yield acyl hydrazones in presence of mild base K2CO3 and low-cost Co(OAc)2·4H2O as catalyst. This method shows good functional group tolerance with good to excellent yield of products. Furthermore, some of the resulting acyl hydrazones have been used as synthetic precursors and explored in various post-synthetic modifications to afford N-heterocyclic compounds. Furthermore, photoswitchable properties of few synthesized acyl hydrazones are also explored using their E/Z isomerization around the C=N bond, as realized by high-pressure liquid chromatography (HPLC) and UV-vis spectroscopic studies.

Leveraging the electrochemical nitrogen reduction reaction (NRR) presents a paradigm shift towards environmentally benign ammonia production operating under ambient conditions. This review encapsulates the forefront of research on Ru- and Mo-based electrocatalysts dedicated to the NRR. Through a meticulous examination, we chronicle recent advancements, harmonizing theoretical insights with empirical findings to provide a comprehensive perspective on the evolution of ammonia synthesis techniques.

Abstract

Ammonia (NH₃), a cornerstone in the chemical industry, has historically been pivotal for producing various valuable products, notably fertilizers. Its significance is further underscored in the modern energy landscape, where NH₃ is seen as a promising medium for hydrogen storage and transportation. However, the conventional Haber–Bosch process, which accounts for approximately 170 million ton of NH₃ produced globally each year, is energy-intensive and environmentally damaging. The electrochemical nitrogen reduction reaction (NRR) emerges as a sustainable alternative that operates in ambient conditions and uses renewable energy sources. Despite its potential, the NRR faces challenges, including the inherent stability of nitrogen and its competition with the hydrogen evolution reaction. Transition metals, especially ruthenium (Ru) and molybdenum (Mo), have demonstrated promise as catalysts, enhancing the efficiency of the NRR. Ru excels in catalytic activity, while Mo offers robustness. Strategies like heteroatom doping are being pursued to mitigate NRR challenges, especially the competing hydrogen evolution reaction. This review delves into the advancements of Ru and Mo-based catalysts for electrochemical ammonia synthesis, elucidating the NRR mechanisms, and championing the transition towards a greener ammonia economy. It also seeks to elucidate the core principles underpinning the NRR mechanism. This shift aims not only to address challenges inherent to traditional production methods but also to align with the overarching goals of global sustainability.

A sustainable and metal-free protocol has been described for the reduction of unprotected indoles. The catalytic system consists of B(C6F5)3 and THF as a Lewis acid-base pair that can activate the B–H bond of pincolborane (HBpin). The catalytic system encompasses a broad substrate scope. Control experiments were conducted to understand the possible catalytic intermediates involved during the present protocol.

This review explores the potential of biomass-derived activated carbon (AC) as a pivotal solution for hydrogen storage challenges. Highlighting its eco-friendliness, cost-effectiveness, and superior adsorption qualities, the work navigates through the synthesis and characterization methodologies of AC. The emphasis on the advantages of biomass sources, coupled with a deep dive into hydrogen uptake and release capacities, sets the stage for future innovations in sustainable hydrogen storage.

Abstract

The increasing global energy demand, which is being driven by population growth and urbanization, necessitates the exploration of sustainable energy sources. While traditional energy generation predominantly relies on fossil fuels, it also contributes to alarming CO₂ emissions. Hydrogen has emerged as a promising alternative energy carrier with its zero-carbon emission profile. However, effective hydrogen storage remains a challenge. When exposed to hydrogen, conventional metallic vessels, once considered to be the primary hydrogen carriers, are prone to brittleness-induced cracking. This has spurred interest in alternative storage solutions, particularly porous materials like metal-organic frameworks and activated carbon (AC). Among these, biomass-derived AC stands out for its eco-friendly nature, cost-effectiveness, and optimal adsorption properties. This review offers a comprehensive overview of recent advancements in the synthesis, characterization, and hydrogen storage capabilities of AC. The unique benefits of biomass-derived sources are highlighted, as is the pivotal role of chemical and physical activation processes. Furthermore, we identify existing challenges and propose future research directions in AC-based hydrogen storage. This compilation aims to serve as a foundation for potential innovations in sustainable hydrogen storage solutions.

A class of 2-hydroxypyridine based ligands are explored to achieve enhanced catalytic activity for ortho-C-H bond activation/arylation reaction over [(η6-p-cymene)RuCl2]2 catalyst in water. Extensive studies using a series of substituted 2-hydroxypyridine based ligands (L1 – L6) inferred that 5-trifluoromethyl-2-hydroxypyridine (L6) exhibited favorable effects to enhance the catalytic activity of Ru(II) catalyst for ortho C-H bond arylation of 2-phenylpyridine by 8 folds compared to those performed without ligands. The (η6-p-cymene)Ru – L6 system also exhibited enhanced catalytic activity for ortho C-H bond arylation of 2-phenylpyridine using a variety of aryl halides. NMR and mass investigations inferred the presence of several ligand coordinated Ru(II) species, suggesting the involvement of these species in C-H bond activation reaction. Further in concurrence with the experimental findings, the density functional theory (DFT) calculations also evidenced the prominent role of 2-hydroxypyridine based ligands in Ru(II) catalyzed C-H bond arylation of 2-phenylpyridine with lower energy barrier for the C-H activation step.

A novel covalent DNA-encoded chemical library (DEL) selection method was developed by utilizing o-nitrobenzyl alcohol (o-NBA), a photo-activated lysine-selective crosslinker. Covalent capture of ligand-target interactions was achieved featuring improved crosslinking efficiency and site-specificity.

Abstract

Covalent crosslinking probes have arisen as efficient toolkits to capture and elucidate biomolecular interaction networks. Exploiting the potential of crosslinking in DNA-encoded chemical library (DEL) selection methods significantly boosted bioactive ligand discovery in complex physiological contexts. Herein, we incorporated o-nitrobenzyl alcohol (o-NBA) as a photo-activated lysine-selective crosslinker into divergent DEL formats and achieved covalent capture of ligand-target interactions featuring improved crosslinking efficiency and site-specificity. In addition, covalent DEL selection was realized with the modularly designed o-NBA-functionalized mock libraries.

We demonstrated the first sequential synthesis of gem-selenoborylation via the diboration of aldehydes and ketones. The selenation of the α-oxyl alkyl boronates was successfully achieved providing a series of synthetically valuable α-seleno alkyl boronates with good functional group tolerance.

Abstract

A method has been described for accessing α-seleno alkyl boronates. The selenoboration was achieved via the diboration of carbonyl compounds to give α-oxyl boronates, which then undergo 1,2-metalate rearrangement in the presence of lithium selenolates and trifluoroacetic anhydride (TFAA). A variety of structurally diverse substrates were compatible with this protocol and efficiently provides difunctionalized products from simple starting materials. The presence of the boronic ester in the resulting organoselenium compounds serves as a versatile synthetic handle for various functionalizations. Mechanistic studies revealed that the binding of selenium nucleophile to both the boron centers in α-oxyl boronate esters.

Germylyne complex [Cp*(OC)2Cr≡Ge{C(SiMe3)3}] (1) reacted with methyl vinyl ketone to give an η3-allyl complex 2 with an oxagermacyclopentenyl ring. An analogous η3-allyl complex 3 with a germacyclopentenyl ring was obtained by the reaction with butadiene, a non-polar conjugated molecule, under photoirradiation. These reactions are accompanied by cleavage of the Cr≡Ge triple bond. On the other hand, the reactions of complex 1 with alkynes under photoirradiation resulted in clean substitution of a CO ligand of 1 to afford (η2-alkyne)germylyne complexes, where the Cr≡Ge triple bond  is intact.