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Themed collection Small Molecule Activation

40 items
Editorial

Small molecule activation

Welcome to this themed issue of Dalton Transactions entitled “Small molecule activation”.

Graphical abstract: Small molecule activation
From the themed collection: Small Molecule Activation
Perspective

Insights into small molecule activation by multinuclear first-row transition metal cyclophanates

The rational design of trimetallic transition metal clusters supported by a trinucleating cyclophane ligand, L3−, and the reactivities of these complexes with dinitrogen and carbon dioxide are discussed.

Graphical abstract: Insights into small molecule activation by multinuclear first-row transition metal cyclophanates
From the themed collection: Small Molecule Activation
Perspective

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

While β-diketiminate (BDI or ‘nacnac’) ligands have been widely adopted to stabilize a wide range of metal ions in multiple oxidation states and coordination numbers, in several occurrences these ligands do not behave as spectators and participate in reactivity.

Graphical abstract: On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds
From the themed collection: Small Molecule Activation
Open Access Perspective

Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges

Catalysts for the oxidation of water are a vital component of solar energy to fuel conversion technologies. This Perspective summarizes recent advances in the field of designing homogeneous water oxidation catalysts (WOCs) based on Mn, Fe, Co and Cu.

Graphical abstract: Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges
From the themed collection: Small Molecule Activation
Communication

Nitrous oxide activation by a cobalt(II) complex for aldehyde oxidation under mild conditions

A new cobalt(II) complex reacts with N2O under mild conditions and it catalytically performs the oxidation of aldehydes.

Graphical abstract: Nitrous oxide activation by a cobalt(ii) complex for aldehyde oxidation under mild conditions
From the themed collection: Small Molecule Activation
Communication

Hydrogen peroxide activation by fluorophilic polyoxotungstates for fast and selective oxygen transfer catalysis

Polyoxometalate (POM)-based polyanionic fluorosurfactants self-assemble in hexafluoroisopropanol (HFIP) and activate hydrogen peroxide (H2O2), yielding efficient epoxidation of terminal alkenes.

Graphical abstract: Hydrogen peroxide activation by fluorophilic polyoxotungstates for fast and selective oxygen transfer catalysis
From the themed collection: Small Molecule Activation
Communication

Aerobic epoxidation catalysed by transition metal substituted polyfluorooxometalates

Polyfluorooxometalates with a nitro ligands, Q9[NaH2CuII(NO2)W17F6O55], are oxygen donors for epoxidation of alkenes and catalytic with O2 as terminal oxidant.

Graphical abstract: Aerobic epoxidation catalysed by transition metal substituted polyfluorooxometalates
From the themed collection: Small Molecule Activation
Open Access Communication

A cobalt(II) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions

In addition to imidometal [Mn+[double bond, length as m-dash]NR] units, transient metal–iminoiodane [M(n−2)+−N(R)[double bond, length as m-dash]IPh] adducts have been demonstrated as a possible “second oxidant” responsible for the imido group transfer reactivity.

Graphical abstract: A cobalt(ii) iminoiodane complex and its scandium adduct: mechanistic promiscuity in hydrogen atom abstraction reactions
From the themed collection: Small Molecule Activation
Communication

Photochemical and electrochemical catalytic reduction of CO2 with NHC-containing dicarbonyl rhenium(I) bipyridine complexes

Efficient photochemical and electrochemical CO2-to-CO conversion using the N,O and N,S-NHC-containing dicarbonyl rhenium(I) bipyridine complexes is described.

Graphical abstract: Photochemical and electrochemical catalytic reduction of CO2 with NHC-containing dicarbonyl rhenium(i) bipyridine complexes
From the themed collection: Small Molecule Activation
Communication

Divergent reactivity of platinum(II) and palladium(II) methylperoxo complexes and the formation of an unusual hemi-aminal complex

The 6,6′′-diaminoterpyridine palladium(II) methylperoxo complex eliminates methyl hydroperoxide and reacts with acetone to form a novel hemi-aminal palladium complex, whereas the analogous platinum(II) complex generates formaldehyde and a platinum(II) hydroxo complex.

Graphical abstract: Divergent reactivity of platinum(ii) and palladium(ii) methylperoxo complexes and the formation of an unusual hemi-aminal complex
From the themed collection: Small Molecule Activation
Communication

Highly efficient dehydrogenation of formic acid in aqueous solution catalysed by an easily available water-soluble iridium(III) dihydride

Water-soluble cis-mer-[IrH2Cl(mtppms)3] selectively dehydrogenated formic acid with a TOF of 298 000 h−1, a final pressure of 140 bar, and a TONmax of 674 000.

Graphical abstract: Highly efficient dehydrogenation of formic acid in aqueous solution catalysed by an easily available water-soluble iridium(iii) dihydride
From the themed collection: Small Molecule Activation
Communication

A mononuclear nonheme cobalt(III)–hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions

A mononuclear nonheme cobalt(III)–hydroperoxide complex bearing a tetramethylated cyclam ligand, which is synthesized by the protonation of its corresponding cobalt(III)–peroxide complex, exhibits an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.

Graphical abstract: A mononuclear nonheme cobalt(iii)–hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions
From the themed collection: Small Molecule Activation
Communication

Activation of CS2 by a “masked” terminal nickel sulfide

Activation of carbon disulfide (CS2) by “masked” terminal nickel sulfide, [K(18-crown-6)][(LtBu)Ni(S)], gives a trithiocarbonate complex. This result confirms the nucleophilicity of the sulfide ligand and expands the scope of reactivity for late metal sulfides.

Graphical abstract: Activation of CS2 by a “masked” terminal nickel sulfide
Paper

Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis

A systematic study on iminopyridine palladium complexes demonstrates the relationship among NMR chemical shifts, ligand donor capability and catalytic performances.

Graphical abstract: Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis
From the themed collection: Small Molecule Activation
Paper

Solution or solid – it doesn't matter: visible light-induced CO release reactivity of zinc flavonolato complexes

Two types of zinc flavonolato complexes exhibit similar visible light-induced CO release reactivity in the solution and solid state.

Graphical abstract: Solution or solid – it doesn't matter: visible light-induced CO release reactivity of zinc flavonolato complexes
From the themed collection: Small Molecule Activation
Paper

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N2

The syntheses of new molybdenum dinitrogen complexes supported by the tridentate PEP ligands (E = N, P) prPP(Ph)P (2), prPPHP (3), PN(Ph)P (4) and prPN(Ph)P (5) are reported.

Graphical abstract: Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N2
From the themed collection: Small Molecule Activation
Paper

Mechanistic insights from theory on the reduction of CO2, N2O, and SO2 molecules using tripodal diimine-enolate substituted magnesium(I) dimers

The mechanistic investigation of the reductive coupling vs. reductive disproportionation of CO2 using magnesium(I) dimers bearing tripodal ligands has been carried out using DFT computational methods.

Graphical abstract: Mechanistic insights from theory on the reduction of CO2, N2O, and SO2 molecules using tripodal diimine-enolate substituted magnesium(i) dimers
From the themed collection: Small Molecule Activation
Paper

Dinitrogen binding, P4-activation and aza-Büchner ring expansions mediated by an isocyano analogue of the CpCo(CO) fragment

Synthetic studies targeting an m-terphenyl isocyanide analogue of the unstable 16e, S = 1 complex CpCo(CO) are reported (Cp = η5-C5H5).

Graphical abstract: Dinitrogen binding, P4-activation and aza-Büchner ring expansions mediated by an isocyano analogue of the CpCo(CO) fragment
From the themed collection: Small Molecule Activation
Paper

Complexes of the tripodal phosphine ligands PhSi(XPPh2)3 (X = CH2, O): synthesis, structure and catalytic activity in the hydroboration of CO2

The coordination chemistry of Fe2+, Co2+ and Cu+ ions was explored with the ligands PhSi{CH2PPh2}3 (1) and PhSi{OPPh2}3 (2), so as to evaluate the impact of the electronic properties of the tripodal phosphorus ligands on the structure and reactivity of the corresponding complexes.

Graphical abstract: Complexes of the tripodal phosphine ligands PhSi(XPPh2)3 (X = CH2, O): synthesis, structure and catalytic activity in the hydroboration of CO2
From the themed collection: Small Molecule Activation
Paper

Photoinduced hydrogen evolution with new tetradentate cobalt(II) complexes based on the TPMA ligand

New cobalt(II) complexes based on the TPMA ligand have been synthesized and characterized as molecular catalysts for photoinduced hydrogen evolution.

Graphical abstract: Photoinduced hydrogen evolution with new tetradentate cobalt(ii) complexes based on the TPMA ligand
From the themed collection: Small Molecule Activation
Paper

A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution

A cobalt complex using a bioinspired ligand, that mimics the molybdopterin cofactor, displays very good activity for electrochemical proton reduction in terms of turnover frequency, faradic yields and stability.

Graphical abstract: A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution
From the themed collection: Small Molecule Activation
Open Access Paper

Oxygen activation and catalytic aerobic oxidation by Mo(IV)/(VI) complexes with functionalized iminophenolate ligands

Dioxidomolybdenum(VI) complexes coordinated by functionalized bidentate iminophenolate ligands undergo oxygen atom transfer to PMe3 to yield molybdenum(IV) oxido phosphino species that readily react with molecular O2 to form molybdenum(VI) oxido peroxido complexes.

Graphical abstract: Oxygen activation and catalytic aerobic oxidation by Mo(iv)/(vi) complexes with functionalized iminophenolate ligands
From the themed collection: Small Molecule Activation
Open Access Paper

Synthesis and catalytic applications of 1,2,3-triazolylidene gold(I) complexes in silver-free oxazoline syntheses and C–H bond activation

Novel triazolylidene gold(I) complexes were synthesized and activated by silver-free methodologies to generate catalysts for oxazoline synthesis and the C–H activation of arenes.

Graphical abstract: Synthesis and catalytic applications of 1,2,3-triazolylidene gold(i) complexes in silver-free oxazoline syntheses and C–H bond activation
From the themed collection: Small Molecule Activation
Paper

Activation of heteroallenes by coordinatively unsaturated nickel(II) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (TpPh,Me) ligand

Activation of sulfur containing heteroallenes by nickel(II) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand is described.

Graphical abstract: Activation of heteroallenes by coordinatively unsaturated nickel(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (TpPh,Me) ligand
From the themed collection: Small Molecule Activation
Paper

Inorganic clusters with a [Fe2MoOS3] core—a functional model for acetylene reduction by nitrogenases

We report the first example of a wholly inorganic mimic of a part of the FeMoco active centre of nitrogenases.

Graphical abstract: Inorganic clusters with a [Fe2MoOS3] core—a functional model for acetylene reduction by nitrogenases
From the themed collection: Small Molecule Activation
Paper

Sterically (un)encumbered mer-tridentate N-heterocyclic carbene complexes of titanium(IV) for the copolymerization of cyclohexene oxide with CO2

Titanium(IV) complexes bearing an unsubstituted tridentate bis(phenolate) N-heterocyclic carbene (NHC) were synthesized and structurally identified.

Graphical abstract: Sterically (un)encumbered mer-tridentate N-heterocyclic carbene complexes of titanium(iv) for the copolymerization of cyclohexene oxide with CO2
From the themed collection: Small Molecule Activation
Paper

Deposition of tetraferrocenylporphyrins on ITO surfaces for photo-catalytic O2 activation

Tetraferrocenylporphyrins have been successfully deposited on ITO electrodes for O2 photo-catalytic activation.

Graphical abstract: Deposition of tetraferrocenylporphyrins on ITO surfaces for photo-catalytic O2 activation
From the themed collection: Small Molecule Activation
Paper

Effective bromo and chloro peroxidation catalysed by tungsten(VI) amino triphenolate complexes

Amino triphenolate tungsten(VI) complexes have been prepared and they proved to be efficient catalysts in haloperoxidation reactions using hydrogen peroxide as a terminal oxidant and inorganic sources of halides.

Graphical abstract: Effective bromo and chloro peroxidation catalysed by tungsten(vi) amino triphenolate complexes
From the themed collection: Small Molecule Activation
Open Access Paper

Small-molecule activation at Au(III): metallacycle construction from ethylene, water, and acetonitrile

Incorporation of the simple, readily available, building blocks ethylene, water and acetonitrile into Au(tpy)(OCOCF3)2 (tpy = 2-(p-tolyl)pyridine) in a one-step reaction leads to high yields of a new 6-membered ring gold(III) metallacycle complex.

Graphical abstract: Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile
From the themed collection: Small Molecule Activation
Paper

Heterodinuclear Ni(II) and Cu(II) Schiff base complexes and their activity in oxygen reduction

New hetero- and homo-dinuclear Cu/Ni complexes electropolymerise potentiodynamically on glassy carbon electrodes and the polymers reduce dioxygen in water.

Graphical abstract: Heterodinuclear Ni(ii) and Cu(ii) Schiff base complexes and their activity in oxygen reduction
From the themed collection: Small Molecule Activation
Paper

Functional models of nonheme diiron enzymes: kinetic and computational evidence for the formation of oxoiron(IV) species from peroxo-diiron(III) complexes, and their reactivity towards phenols and H2O2

The reactivity of peroxo adducts towards H2O2 and phenols as functional catalase and RNR-R2 mimics is described.

Graphical abstract: Functional models of nonheme diiron enzymes: kinetic and computational evidence for the formation of oxoiron(iv) species from peroxo-diiron(iii) complexes, and their reactivity towards phenols and H2O2
From the themed collection: Small Molecule Activation
Paper

Low coordinate iron derivatives stabilized by a β-diketiminate mimic. Synthesis and coordination chemistry of enamidophosphinimine scaffolds to generate diiron dinitrogen complexes

The reduction of the iron enamido-phosphinimine complex under N2 leads to dinitrogen activation and cleavage of the phosphinimine linkage to generate a di-iron complex with a bridging imido moiety.

Graphical abstract: Low coordinate iron derivatives stabilized by a β-diketiminate mimic. Synthesis and coordination chemistry of enamidophosphinimine scaffolds to generate diiron dinitrogen complexes
From the themed collection: Small Molecule Activation
Paper

Nickel-catalyzed release of H2 from formic acid and a new method for the synthesis of zerovalent Ni(PMe3)4

Ni(PMe3)4, which can be obtained by reaction of either Ni(py)4(O2CH)2 or Ni(O2CH)2·2H2O with PMe3, serves as a catalyst for the release of H2 from formic acid.

Graphical abstract: Nickel-catalyzed release of H2 from formic acid and a new method for the synthesis of zerovalent Ni(PMe3)4
From the themed collection: Small Molecule Activation
Paper

Tailored design of ruthenium molecular catalysts with 2,2′-bypyridine-6,6′-dicarboxylate and pyrazole based ligands for water oxidation

A series of tailor-designed Ruthenium based water oxidation catalysts have been synthesized. By fine tuning of the catalyst structure, the turnover frequency was increased up to 500 s−1 and the stability over 6000 turnovers.

Graphical abstract: Tailored design of ruthenium molecular catalysts with 2,2′-bypyridine-6,6′-dicarboxylate and pyrazole based ligands for water oxidation
From the themed collection: Small Molecule Activation
Paper

High catalytic abilities of binuclear rhenium(I) complexes in the photochemical reduction of CO2 with a ruthenium(II) photosensitiser

Photocatalytic systems for CO2 reduction using a Ru(II) photosensitiser and dinuclear Re(I) diimine tricarbonyl complexes (Re(n)Re), in which diimine ligands are connected by alkyl chains of various lengths (–CnH2n–: n = 2, 3, 4, 6, 14), as catalysts were investigated.

Graphical abstract: High catalytic abilities of binuclear rhenium(i) complexes in the photochemical reduction of CO2 with a ruthenium(ii) photosensitiser
From the themed collection: Small Molecule Activation
Open Access Paper

Aluminium salabza complexes for fixation of CO2 to organic carbonates

A highly stable and easy to synthesize aluminium complex bearing a flexible N2O2-donor salabza ligand (N,N′-bis(salicylene)-2-aminobenzylamine) in combination with tetrabutylammonium bromide forms an active binary catalytic system for the cycloaddition of CO2 to epoxides (TOFs 120–3434 h−1) under mild conditions (10 bar, 80 °C) and low catalyst loadings (0.05–0.2 mol%).

Graphical abstract: Aluminium salabza complexes for fixation of CO2 to organic carbonates
From the themed collection: Small Molecule Activation
Paper

Electrophilic phosphonium cations (EPCs) with perchlorinated-aryl substituents: towards air-stable phosphorus-based Lewis acid catalysts

A series of fluorophosphonium cations incorporating (C6Cl5) substituents, [Ph2PF(C6Cl5)][B(C6F5)4] 8, [PhPF(C6Cl5)2][B(C6F5)4] 9, and [(C6F5)PF(C6Cl5)2][B(C6F5)4] 10, were prepared and tested for air stability and catalytic activity.

Graphical abstract: Electrophilic phosphonium cations (EPCs) with perchlorinated-aryl substituents: towards air-stable phosphorus-based Lewis acid catalysts
From the themed collection: Small Molecule Activation
Paper

Raman spectroscopy of the N–N bond in rare earth dinitrogen complexes

Raman spectra have been collected on single crystals of over 20 different rare earth complexes containing reduced dinitrogen ligands to determine if these data will correlate with periodic properties or relative stability.

Graphical abstract: Raman spectroscopy of the N–N bond in rare earth dinitrogen complexes
Paper

Copper-induced ammonia N–H functionalization

The TpMsCu core has been found to bind ammonia as well as to promote stoichiometric or catalytic modification of the ammonia N–H bond.

Graphical abstract: Copper-induced ammonia N–H functionalization
From the themed collection: Small Molecule Activation
Paper

Electrocatalytic reduction of CO2 by thiophene-substituted rhenium(I) complexes and by their polymerized films

Three novel Re complexes with thiophene substituted bipyridine ligands were electropolymerized on GCE surface by oxidation. The surface-modified electrodes were tested for electrocatalytic CO2 reduction.

Graphical abstract: Electrocatalytic reduction of CO2 by thiophene-substituted rhenium(i) complexes and by their polymerized films
From the themed collection: Small Molecule Activation
40 items

About this collection

Small molecule activation constitutes one of the main frontiers of inorganic and organometallic chemistry, with much effort directed towards the development of new processes for the selective and sustainable transformation of abundant small molecules such as H2O, NH3, N2, O2, CO, or CO2 into high-value chemical feedstocks and energy resources.

This themed issue focuses on homogenously catalysed activation of small molecules, as well as stoichiometric reactions that further our understanding towards such ends. The manuscripts included cover many aspects of small molecule activation including: organometallic chemistry, (electro)catalysis, photochemistry, mechanistic studies, spectroscopy, synthesis, and developments in materials science.

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