Themed collection Small Molecule Transformations of Energy Relevance

18 items
Communication

Low-valent group 6 metals/Al(C6F5)3 donor–acceptor systems for CO2 activation and cleavage

Donor–acceptor systems for CO2 activation combining a formally zero-valent group 6 metal as the donor with the Lewis acid Al(C6F5)3 (AlCF) are reported.

Graphical abstract: Low-valent group 6 metals/Al(C6F5)3 donor–acceptor systems for CO2 activation and cleavage
Communication

Reduction of CS2 to an ethanetetrathiolate by a hydride-bridged uranium–iridium heterobimetallic complex

We report the synthesis of a heterobimetallic U(III)–Ir species which reacts with CS2 to form the novel ethanetetrathiolate fragment via hydride insertion and C–C coupling.

Graphical abstract: Reduction of CS2 to an ethanetetrathiolate by a hydride-bridged uranium–iridium heterobimetallic complex
From the themed collection: ChemComm 60th Anniversary Collection
Open Access Accepted Manuscript - Communication

Csp2–H/F bond activation and borylation with low valent iron

Open Access Communication

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.

Graphical abstract: Synthesis of a potassium capped terminal cobalt–oxido complex
Open Access Communication

A neutral crystalline imino-substituted silyl radical

The neutral three-coordinated imino(silyl)silyl radical was isolated from the reaction of ItBuN-SiBr3 with NaSitBu2Me. The radical was fully characterized by SC-XRD and EPR spectroscopy and supported by quantum chemical calculations.

Graphical abstract: A neutral crystalline imino-substituted silyl radical
Open Access Communication

CO2 cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes

A novel Ta/Os complex [Ta(CH2tBu)3(μ-H)3OsCp*], and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], efficiently cleave CO2 under mild conditions, forming tantalum oxo species and CpIr(CO)H2 or CpOs(CO)H3.

Graphical abstract: CO2 cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes
From the themed collection: 2024 Pioneering Investigators
Communication

Hydrazido complexes prepared by methylation of an anionic end-on bridging dinitrogen dititanium complex

Stepwise methylation of end-on bridging dinitrogen to a hydrazido ligand to a pentamethylhydrazinium salt is mediated by a titanium complex.

Graphical abstract: Hydrazido complexes prepared by methylation of an anionic end-on bridging dinitrogen dititanium complex
Open Access Communication

Efficient carbene transfer reactivity mediated by Fe(II) complexes supported by bulky alkoxides

The reaction of Fe(OR)2(THF)2 (OR = bulky alkoxide ligand) with PhIC(CO2Me)2 results in the formation of reactive remote carbene/vinyl radical intermediate that undergoes facile cyclopropanation or dimerization.

Graphical abstract: Efficient carbene transfer reactivity mediated by Fe(ii) complexes supported by bulky alkoxides
Communication

Dinitrogen activation at chromium by photochemically induced CrII–C bond homolysis

Exposure of (POCOPtBu)Cr(Bn) to 427 nm blue light under 1 atm N2 promoted Cr–CBn bond homolysis and led to N2 activation forming [(POCOPtBu)Cr]2(μ-N2).

Graphical abstract: Dinitrogen activation at chromium by photochemically induced CrII–C bond homolysis
Communication

Ni2P active site ensembles tune electrocatalytic nitrate reduction selectivity

Intrinsic active site ensembles on Ni2P nanocrystal surfaces direct the selective reduction of nitrate to ammonia through the potential-dependent co-adsorption of H* and NOx*.

Graphical abstract: Ni2P active site ensembles tune electrocatalytic nitrate reduction selectivity
From the themed collection: ChemComm 60th Anniversary Collection
Open Access Communication

Appropriation of group II metals: synthesis and characterisation of the first alkaline earth metal supported transition metal carbonite complexes

Complexes where magnesium and calcium ions assist CO2 activation at nickel centres have been accessed and were found to enter into Schlenk-type equilibria.

Graphical abstract: Appropriation of group II metals: synthesis and characterisation of the first alkaline earth metal supported transition metal carbonite complexes
Communication

A vertically-stacked MXene/rGO composite membrane for highly efficient H2/CO2 separation

In comparison to the horizontally stacked membrane, the bioinspired vertical channels offered more direct and less convoluted paths, resulting in an order of magnitude increase in hydrogen permeability.

Graphical abstract: A vertically-stacked MXene/rGO composite membrane for highly efficient H2/CO2 separation
Communication

Catalytic dinitrogen reduction to hydrazine and ammonia using Cr(N2)2(diphosphine)2 complexes

Cr(N2)2(diphosphine)2 complexes catalyze the reduction of dinitrogen at room temperature using SmI2 and ethylene glycol or H2O to form hydrazine and ammonia.

Graphical abstract: Catalytic dinitrogen reduction to hydrazine and ammonia using Cr(N2)2(diphosphine)2 complexes
Open Access Communication

Temperature induced single-crystal to single-crystal transformation of uranium azide complexes

A temperature-induced single-crystal to single-crystal transformation was observed in monoanionic N–P ligand-supported uranium azide complexes.

Graphical abstract: Temperature induced single-crystal to single-crystal transformation of uranium azide complexes
Open Access Communication

Post transition metal substituted Keggin-type POMs as thin film chemiresistive sensors for H2O and CO2 detection

Chemiresitive sensing allows the affordable and facile detection of small molecules such as H2O and CO2.

Graphical abstract: Post transition metal substituted Keggin-type POMs as thin film chemiresistive sensors for H2O and CO2 detection
From the themed collection: Chemical Communications HOT Articles 2024
Communication

Steric control of Mg–Mg bond formation vs. N2 activation in the reduction of bulky magnesium diamide complexes

Reduction of a bulky diamido-magnesium(II) complex has yielded the potassium salt of a dimagnesium(I) dianion, whereas prior reduction of a bulkier analogue gave an activated N2 complex. The relevance of ligand bulk in these processes is discussed.

Graphical abstract: Steric control of Mg–Mg bond formation vs. N2 activation in the reduction of bulky magnesium diamide complexes
From the themed collection: Chemical Communications HOT Articles 2024
Open Access Paper

Bio-inspired copper complexes with Cu2S cores: (solvent) effects on oxygen reduction reactions

A new mixed-valent Cu complex (6) allows for the systematic study of oxygen reduction reactions in acetonitrile/acetone and comparison with its parent (1). Kinetics and selectivity are influenced, suggesting changes at the chemical structure of (6).

Graphical abstract: Bio-inspired copper complexes with Cu2S cores: (solvent) effects on oxygen reduction reactions
Paper

Reactivity of low-valent nickel carbonyl species supported by acridane based PNP ligands towards iodoalkanes

Selective C–C coupling occurs at the sterically well-protected nickel(0 or I)–CO site.

Graphical abstract: Reactivity of low-valent nickel carbonyl species supported by acridane based PNP ligands towards iodoalkanes
18 items

About this collection

Reactions of small molecules (e.g., N2, H2, CO, CO2, O2, NH3, etc.) are fundamental to societal challenges associated with energy and the environment. Removal of certain small molecules from the atmosphere is key to environmental remediation, while development of catalytic redox processes of small molecules is central to renewable energy generation and storage. Valorisation of small molecules can also improve efficiency and sustainability of industrial processes. Through all these research directions, understanding the mechanisms for small molecule activation provides insight into fundamental principles of chemical reactivity. 

Guest edited by Professor Neal Mankad (University of Illinois Chicago, USA) and Professor Marinella Mazzanti (EPFL, Switzerland), this joint ChemComm and Dalton Transactions collection covers research on stoichiometric and catalytic transformations of small molecules of relevance to energy and the environment, emphasising the application of molecular compounds but also including solid state materials in small molecule transformations.


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