Themed collection Inorganic Reaction Mechanisms
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Inorganic reaction mechanisms
Sam de Visser, Jonathan Rourke and Kylie Vincent introduce this Dalton Transactions themed collection on inorganic reaction mechanisms.
Dalton Trans., 2020,49, 4597-4598
https://doi.org/10.1039/D0DT90059A
Inorganic reaction mechanisms. A personal journey
This review describes a personal journey over the past two decades highlighting experimental and computational mechanistic studies in inorganic chemistry performed with numerous PhD students, post-docs, visiting scientists and colleagues from abroad.
Dalton Trans., 2020,49, 4599-4659
https://doi.org/10.1039/C9DT04620H
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Vibrational properties of heme-nitrosoalkane complexes in comparison with those of their HNO analogs, and reactivity studies towards nitric oxide and Lewis acids
Six-coordinate heme-RNO complexes, [Fe(Porph)(L)(RNO)] (Porph = TPP, 3,5-Me-BAFP; R= iPr, Ph), were prepared and structurally and spectroscopically characterized. The reactivity of the complexes towards NO and different Lewis acids was then explored.
Dalton Trans., 2024,53, 13906-13924
https://doi.org/10.1039/D4DT01632G
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Twinned versus linked organometallics - bimetallic “half-baguette” pentalenide complexes of Rh(I)
Bimetallic “baguette” versions of the popular CpRh(I) “sandwich” complexes have been synthesised with a tetraarylated pentalenide. The factors leading to syn versus anti metallation have been investigated and the scope of ligand substitution is explored.
Dalton Trans., 2024,53, 5881-5899
https://doi.org/10.1039/D3DT04325H
Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents
A ruthenium phthalocyanine catalyzes the cyclopropanation of olefins (15 substr.) and single carbene insertion into N–H bonds of aromatic, heteroaromatic and aliphatic amines (20 substr.) with high selectivity and under practical reaction conditions.
Dalton Trans., 2021,50, 2023-2031
https://doi.org/10.1039/D0DT04090H
Coupled electron and proton transfer in the piperidine drug metabolism pathway by the active species of cytochromes P450
KS-DFT and MSDFT studies reveal a novel CEPT step that triggers ring contraction of piperidines by P450.
Dalton Trans., 2020,49, 11099-11107
https://doi.org/10.1039/C9DT03056E
Kinetic studies on the reaction of NO with iron(II) complexes using low temperature stopped-flow techniques
Quite different reaction mechanisms were observed in a kinetic study of NO binding to iron(II) complexes.
Dalton Trans., 2020,49, 9480-9486
https://doi.org/10.1039/D0DT01764G
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Mechanism of CO2 conversion to methanol over Cu(110) and Cu(100) surfaces
Density functional methods are applied to explore the reaction mechanism for CO2 hydrogenation to methanol over low-index Cu surfaces, namely Cu(110) and Cu(100).
Dalton Trans., 2020,49, 8478-8497
https://doi.org/10.1039/D0DT00754D
Sluggish reactivity by a nonheme iron(IV)-tosylimido complex as compared to its oxo analogue
A comparative spectroscopic and computational study of reactivity between ferryl-tosylimido and ferryl-oxo complexes of two biomimetic model systems. The Fe(IV)-tosylimido complex was found to be sluggish in comparison to its fellow oxo counterpart.
Dalton Trans., 2020,49, 5921-5931
https://doi.org/10.1039/D0DT00018C
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Catalytic dioxygen reduction mediated by a tetranuclear cobalt complex supported on a stannoxane core
The synthesis, spectroscopic characterization and DFT calculations of a tetranuclear cobalt complex supported on a stannoxane core, and its catalytic O2-reduction ability are reported.
Dalton Trans., 2020,49, 6065-6073
https://doi.org/10.1039/D0DT00475H
Time-resolved infra-red spectroscopy reveals competitive water and dinitrogen coordination to a manganese(I) carbonyl complex
Photolysis of [Mn(C^N)(CO)4] (C^N = bis-(4-methoxyphenyl)methanimine) in heptane solution results in ultra-fast CO dissociation and ultimate formation of a rare Mn-containing dinitrogen complex fac-[Mn(C^N)(CO)3(N2)].
Dalton Trans., 2020,49, 5463-5470
https://doi.org/10.1039/C9DT04878B
Ligand-based electronic effects on the electrocatalytic hydrogen production by thiosemicarbazone nickel complexes
This work reports on the synthesis and characterization of a series of mononuclear thiosemicarbazone nickel complexes that display significant catalytic activity for hydrogen production in DMF using trifluoroacetic acid as the proton source.
Dalton Trans., 2020,49, 5064-5073
https://doi.org/10.1039/C9DT04775A
Regioselectivity of hyoscyamine 6β-hydroxylase-catalysed hydroxylation as revealed by high-resolution structural information and QM/MM calculations
Crystal structures and computational results reveal how Hyoscyamine 6β-hydroxylase targets its oxidative power at the C6 position of the tropane ring while sparing the nearby C7 site.
Dalton Trans., 2020,49, 4454-4469
https://doi.org/10.1039/D0DT00302F
Computational studies of DNA base repair mechanisms by nonheme iron dioxygenases: selective epoxidation and hydroxylation pathways
A detailed QM/MM and DFT study into the structure and reactivity of AlkB repair enzymes with alkylated DNA bases is reported. In particular, we investigate the aliphatic hydroxylation and CC epoxidation mechanisms of the enzymes by a high-valent iron(IV)–oxo intermediate.
Dalton Trans., 2020,49, 4266-4276
https://doi.org/10.1039/D0DT00007H
Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound
A commercially available iron readily engages in catalytic Si–O and Si–N bond formation under visible light irradiation.
Dalton Trans., 2020,49, 2972-2978
https://doi.org/10.1039/C9DT04870G
Spin state and reactivity of iron(IV)oxido complexes with tetradentate bispidine ligands
The iron(IV)oxido complex [(bispidine)FeIVO(Cl)]+ is shown by experiment and high-level DLPNO-CCSD(T) quantum-chemical calculations to be an extremely short-lived and very reactive intermediate-spin (S = 1) species.
Dalton Trans., 2020,49, 2888-2894
https://doi.org/10.1039/C9DT04578C
Peroxocobalt(III) species activates nitriles via a superoxocobalt(II) diradical state
The dioxygenation of nitriles by [CoIII(TBDAP)(O2)]+ (TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane) is investigated using DFT-calculations.
Dalton Trans., 2020,49, 2819-2826
https://doi.org/10.1039/D0DT00042F
Steric and electronic effects on acetate-assisted cyclometallation of 2-phenylpyridines at [MCl2Cp*]2 (M = Ir, Rh)
Kinetic and thermodynamic selectivities are opposite: steric and electronic factors control ortho : para selectivity (R2).
Dalton Trans., 2020,49, 2680-2686
https://doi.org/10.1039/C9DT04581C
Discovery and mechanistic investigation of Pt-catalyzed oxidative homocoupling of benzene with PhI(OAc)2
Pt-catalyzed direct coupling of benzene to biphenyl using PhI(OAc)2 as an oxidant in the absence of any acid as a co-solvent or co-catalyst was mechanistically investigated.
Dalton Trans., 2020,49, 2477-2486
https://doi.org/10.1039/C9DT04261J
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Routes of iron entry into, and exit from, the catalytic ferroxidase sites of the prokaryotic ferritin SynFtn
This work describes the identification of two residues, D137 and E62, that are critical for, respectively, the transport of Fe2+ into, and Fe3+ out of, the catalytic sites of a prokaryotic ferritin.
Dalton Trans., 2020,49, 1545-1554
https://doi.org/10.1039/C9DT03570B
A subtle structural change in the distal haem pocket has a remarkable effect on tuning hydrogen peroxide reactivity in dye decolourising peroxidases from Streptomyces lividans
A subtle positional shift of the distal haem pocket aspartate in two dye decolourising peroxidase homologs has a remarkable effect on their reactivity with H2O2.
Dalton Trans., 2020,49, 1620-1636
https://doi.org/10.1039/C9DT04583J
Tandem deoxygenative hydrosilation of carbon dioxide with a cationic scandium hydridoborate and B(C6F5)3
A scandium hydridoborate complex supported by the dianionic pentadentate ligand B2Pz4Py is prepared via hydride abstraction from the previously reported scandium hydride complex with tris-pentafluorophenyl borane.
Dalton Trans., 2020,49, 95-101
https://doi.org/10.1039/C9DT04323C
Base-controlled mechanistic divergence between iron(IV)-oxo and iron(III)-hydroperoxo in the H2O2 activation by a nonheme iron(II) complex
An FeII complex reacts with excess H2O2 in the presence of sub-stoichiometric NEt3 to give FeIV(O) and FeIII(OOH) reactive species following a base-dependent and a base-independent pathway, respectively.
Dalton Trans., 2019,48, 17045-17051
https://doi.org/10.1039/C9DT03487K
Reactivity patterns of vanadium(IV/V)-oxo complexes with olefins in the presence of peroxides: a computational study
Density functional theory calculations on vanadium-oxo and -peroxo porphyrins are reported and show these systems to be versatile oxidants.
Dalton Trans., 2019,48, 16899-16910
https://doi.org/10.1039/C9DT03048D
Proton-assisted air oxidation mechanisms of iron(II) bis-thiosemicarbazone complexes at physiological pH: a kinetico-mechanistic study
The kinetics of oxidation of different biologically-active FeII bis-thiosemicarbazone complexes in water has been monitored at varying dioxygen concentration, temperature, pressure, and pH.
Dalton Trans., 2019,48, 16578-16587
https://doi.org/10.1039/C9DT03557E
On the reaction mechanism of an endoperoxide ring formation by fumitremorgin B endoperoxidase. The right arrangement makes a difference
Computations suggest how the substrate binds within the active site and what is the mechanism of an endoperoxide ring formation.
Dalton Trans., 2019,48, 16211-16221
https://doi.org/10.1039/C9DT02581B
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The role of neutral Rh(PONOP)H, free NMe2H, boronium and ammonium salts in the dehydrocoupling of dimethylamine-borane using the cationic pincer [Rh(PONOP)(η2-H2)]+ catalyst
Cationic σ-dihydrogen, σ-amine-borane and neutral hydride complexes, based upon {Rh(PONOP)}, are all shown play a role in the dehydrocoupling of H3B·NMe2H. Movement between the three is promoted by free amine, NMe2H.
Dalton Trans., 2019,48, 14724-14736
https://doi.org/10.1039/C9DT03358K
About this collection
This special web collection of Dalton Transactions focusses on the field of inorganic reaction mechanisms. Guest edited by Sam de Visser (University of Manchester), Jonathan Rourke (University of Cardiff) and Kylie Vincent (University of Oxford) this collection celebrates 50 years of the Inorganic Reaction Mechanisms Discussion Group and highlights the breadth and depth of the area, paying particular interest to areas of contemporary relevance.