Themed collection Most popular 2024 inorganic chemistry articles


The missing pieces in the catalytic cycle of [FeFe] hydrogenases
Over the years, spectroscopic, electrochemical and structural studies of [FeFe] hydrogenases have provided ‘pieces’ of information to complete the ‘puzzle’ of their catalytic cycle. However, there are still missing pieces that we need to fill in.
Chem. Sci., 2024,15, 14062-14080
https://doi.org/10.1039/D4SC04041D

A decade of lessons in the activation of ArIL2 species
Developments in methods to increase the oxidative capacity of ArIL2 reagents are discussed, with a focus on an understanding of these species' behaviour from the perspective of the iodine.
Chem. Sci., 2024,15, 3784-3799
https://doi.org/10.1039/D3SC06588J

A review of frustrated Lewis pair enabled monoselective C–F bond activation
Functionalisation of polyfluorocarbon positions generally suffers from over-defluorination. Frustrated Lewis pairs (FLPs) offer a unique solution to this problem allowing direct access to a wide range of 2nd generation fluorocarbon products.
Chem. Sci., 2024,15, 2712-2724
https://doi.org/10.1039/D3SC06485A

A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions
Ligand-to-metal charge transfer (LMCT) excited states showcase promise in enabling photochemical reactions. This article details design principles to enable low energy LMCT excited states and notable examples that drive
Chem. Sci., 2024,15, 6661-6678
https://doi.org/10.1039/D3SC05268K

An elastic siderophore synthetase and rubbery substrates assemble multimeric linear and macrocyclic hydroxamic acid metal chelators
Enzyme-mediated synthesis using one or a combination of two substrates produced biocombinatorial mixtures of multimeric linear and macrocyclic hydroxamic acid chelators. Screening the pools with Ga(III) or Zr(IV) revealed new coordination chemistry..
Chem. Sci., 2025,16, 2180-2190
https://doi.org/10.1039/D4SC04888A

Phosphoester bond hydrolysis by a discrete zirconium-oxo cluster: mechanistic insights into the central role of the binuclear ZrIV–ZrIV active site
Effective degradation of non-natural phosphate triesters (PTs) widely used in pesticides and warfare agents is of paramount relevance for human and environmental safety, particularly under acidic conditions where they are highly stable.
Chem. Sci., 2024,15, 18008-18021
https://doi.org/10.1039/D4SC03946G

Quantifying variation in cooperative B–H bond activations using Os(II) and Os(III) κ2-N,S-chelated complexes: same, but different
Versatile activation modes of borane have been illustrated utilising MLC in osmium based bis-κ2-N,S-chelated species.
Chem. Sci., 2024,15, 15913-15924
https://doi.org/10.1039/D4SC05092D

Illuminating the multiple Lewis acidity of triaryl-boranes via atropisomeric dative adducts
The emergence of a peculiar molecular phenomenon, the single-centered, but multiple Lewis acidity, is uncovered among Lewis acidic boranes with appropriate steric crowding and symmetry design.
Chem. Sci., 2024,15, 15679-15689
https://doi.org/10.1039/D4SC00925H

Hydrogen atom abstraction as a synthetic route to a square planar CoII complex with a redox-active tetradentate PNNP ligand
Dehydrogenation of the ligand backbone of a bis(amido)bis(phosphine) Co complex is achieved through hydrogen atom abstraction. The new unsaturated backbone of the tetradentate ligand renders the ligand in the resulting Co complex redox-active.
Chem. Sci., 2024,15, 15311-15320
https://doi.org/10.1039/D4SC03364G

(η8-Cyclooctatetraene)(η5-fluorenyl)titanium: a processable molecular spin qubit with optimized control of the molecule–substrate interface
A comprehensive investigation shows that the replacement of a cyclopentadienyl ligand with fluorenyl increases the adsorption energy of the [FluTi(cot)] spin-qubit candidate on Au(111) without loss of spin density toward the surface.
Chem. Sci., 2024,15, 14390-14398
https://doi.org/10.1039/D4SC03290J

Coherent spin-control of S = 1 vanadium and molybdenum complexes
Enabling coherent spin-control in integer spin complexes with molecular color center design.
Chem. Sci., 2024,15, 14016-14026
https://doi.org/10.1039/D4SC03107E

Multicolor photoluminescence of Cu14 clusters modulated using surface ligands
We present effective manipulation of the emissive excited states in a Cu14 cluster through the surface engineering of secondary ligands.
Chem. Sci., 2024,15, 13741-13752
https://doi.org/10.1039/D4SC01566E

Triborane (B3H7)-mediated regioselective substitution reactions of pyridine derivatives
There exists an interplay between borane and a Lewis base in their adducts.
Chem. Sci., 2024,15, 13923-13929
https://doi.org/10.1039/D4SC03109A

Exploring the influence of H-bonding and ligand constraints on thiolate ligated non-heme iron mediated dioxygen activation
The kinetics study herein experimentally demonstrates that an inner-sphere ET mechanism is involved in the conversion of triplet O2 into a powerful oxidant by an RS–Fe complex. Hydrogen-bond donors are shown to destabilize the transition-state.
Chem. Sci., 2024,15, 12710-12720
https://doi.org/10.1039/D4SC02787F

Spontaneous ligand loss by soft landed [Ni(bpy)3]2+ ions on perfluorinated self-assembled monolayer surfaces
[Ni(bpy)3]2+ soft landed on surfaces dissociates spontaneously. Codeposition of stable anions with cations enables preservation of the structure of [Ni(bpy)3]2+.
Chem. Sci., 2024,15, 10770-10783
https://doi.org/10.1039/D4SC02527J

Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation of a stable U(V) sandwich complex
Actinide doping enhances redox chemistry of polyoxomolybdate-alkoxide clusters; the first isolable U(V) polyoxometalate cluster is reported.
Chem. Sci., 2024,15, 11072-11083
https://doi.org/10.1039/D4SC02644F

Mechanistic investigations of the Fe(II) mediated synthesis of squaraines
In situ monitoring and reaction sampling (IR, NMR, EPR, Mössbauer spectroscopy) and structural characterisation of isolable species allows detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes.
Chem. Sci., 2024,15, 9599-9611
https://doi.org/10.1039/D4SC01286K

Re-pairing DNA: binding of a ruthenium phi complex to a double mismatch
The complex [Ru(phen)2phi]2+ creates a bulge site when crystallised with a DNA dodecamer which includes the Pribnow box sequence.
Chem. Sci., 2024,15, 9096-9103
https://doi.org/10.1039/D4SC01448K

Neutral inverse-sandwich rare-earth metal complexes of the benzene tetraanion
Neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion with an [M3+–(C6H6)4−–M3+] core electronic structure were synthesized and characterized. They behave as a four-electron reductant to reduce unsaturated substrates.
Chem. Sci., 2024,15, 8740-8749
https://doi.org/10.1039/D4SC02491E

Insights into mechanistic interpretation of crystalline-state reddish phosphorescence of non-planar π-conjugated organoboron compounds
Benzo[d]dithieno[b,f]borepins exhibited reddish room-temperature phosphorescence (RTP) despite the absence of heavy atoms and oxygen atoms.
Chem. Sci., 2024,15, 8127-8136
https://doi.org/10.1039/D4SC01184H

Pb2(SeO3)(SiF6): the first selenite fluorosilicate with a wide bandgap and large birefringence achieved through perfluorinated group modification
The first selenite fluorosilicate, Pb2(SeO3)(SiF6), modified with perfluorinated groups, features a broad transparency range, large birefringence, high LIDT, and excellent environmental stability, marking it a potential birefringent material.
Chem. Sci., 2024,15, 7104-7110
https://doi.org/10.1039/D4SC01376J

Electronic isomerism in a heterometallic nickel–iron–sulfur cluster models substrate binding and cyanide inhibition of carbon monoxide dehydrogenase
A protein-based model of carbon monoxide dehydrogenase displays distinct X-ray absorption, EPR, and vibrational signatures upon CO and CN− binding that support ligand-dependent electronic rearrangement throughout the nickel–iron–sulfur core.
Chem. Sci., 2024,15, 5916-5928
https://doi.org/10.1039/D4SC00023D

Predicting valence tautomerism in diverse cobalt–dioxolene complexes: elucidation of the role of ligands and solvent
An inexpensive DFT-based strategy has been identified for the prediction of valence tautomerism in neutral and cationic Co–dioxolene complexes, including prediction of the interconversion temperature and variation with solvent.
Chem. Sci., 2024,15, 5694-5710
https://doi.org/10.1039/D3SC04493A

s-Block metal complexes of superbulky (tBu3Si)2N−: a new weakly coordinating anion?
The extremely challenging deprotonation of the amine (tBu3Si)2NH led to a range of s-block metal complexes with superbulky (tBu3Si)2N−. Depending on metal and solvent, (tBu3Si)2N− can be classified as a halogen-free weakly coordinating anion.
Chem. Sci., 2024,15, 4386-4395
https://doi.org/10.1039/D3SC06896J

Discovery of antibacterial manganese(I) tricarbonyl complexes through combinatorial chemistry
To accelerate the discovery of novel metalloantibiotics we applied combinatorial synthesis to the preparation of 420 novel manganese tricarbonyl complexes.
Chem. Sci., 2024,15, 3907-3919
https://doi.org/10.1039/D3SC05326A

Unusual catalytic strategy by non-heme Fe(II)/2-oxoglutarate-dependent aspartyl hydroxylase AspH
The second coordination sphere, Asp721, participates in a hydrogen bond with an iron-coordinated water molecule, thus compensating for the missing facial triad carboxylate in AspH and enabling stereoselective C–H oxidation.
Chem. Sci., 2024,15, 3466-3484
https://doi.org/10.1039/D3SC05974J

The pressure response of Jahn–Teller-distorted Prussian blue analogues
Jahn–Teller (JT) distorted CuII-containing compounds often display interesting structural and functional behaviour upon compression.
Chem. Sci., 2024,15, 3155-3164
https://doi.org/10.1039/D3SC06912E

Metal–carbon bonding in early lanthanide substituted cyclopentadienyl complexes probed by pulsed EPR spectroscopy
We report relaxation and ligand hyperfine effects in an isostructural series of early lanthanide substituted cyclopentadienyl complexes, [Ln(Cptt)3] (Ln = Ce, Nd, Sm; Cptt = C5H3tBu2-1,3), by pulsed EPR spectroscopy.
Chem. Sci., 2024,15, 3003-3010
https://doi.org/10.1039/D3SC06175B

Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis-[Zr6F34]10− clusters
The new zirconium fluoride, K3Ba2Zr6F31, is reported, featuring unprecedented acentric cis-[Zr6F34]10− clusters composed of ZrF8 units, which display a moderate second-harmonic generation response (0.5 × KH2PO4) and short UV cutoff edge (below 200 nm).
Chem. Sci., 2024,15, 2883-2888
https://doi.org/10.1039/D3SC06683E
About this collection
This specially curated collection highlights some of the most popular articles from 2024 in the fields of main group, inorganic, bioinorganic, and organometallic chemistry. The collection presents some outstanding contributions to the field, ranging from optical fluoride materials to insights into [FeFe] hydrogenases, and as with all Chemical Science articles – they are all completely free to access and read. We hope you enjoy browsing through this collection.
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