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Themed collection Inorganic Reaction Mechanisms

25 items
Editorial

Inorganic reaction mechanisms

Sam de Visser, Jonathan Rourke and Kylie Vincent introduce this Dalton Transactions themed collection on inorganic reaction mechanisms.

Graphical abstract: Inorganic reaction mechanisms
From the themed collection: Inorganic Reaction Mechanisms
Perspective

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.

Graphical abstract: Inorganic reaction mechanisms. A personal journey
From the themed collection: 2020 Frontier and Perspective articles
Paper

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.

Graphical abstract: Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Coupled electron and proton transfer in the piperidine drug metabolism pathway by the active species of cytochromes P450
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Kinetic studies on the reaction of NO with iron(ii) complexes using low temperature stopped-flow techniques
From the themed collection: Inorganic Reaction Mechanisms
Open Access Paper

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).

Graphical abstract: Mechanism of CO2 conversion to methanol over Cu(110) and Cu(100) surfaces
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Sluggish reactivity by a nonheme iron(iv)-tosylimido complex as compared to its oxo analogue
From the themed collection: Inorganic Reaction Mechanisms
Open Access Paper

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.

Graphical abstract: Catalytic dioxygen reduction mediated by a tetranuclear cobalt complex supported on a stannoxane core
From the themed collection: Inorganic Reaction Mechanisms
Paper

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)].

Graphical abstract: Time-resolved infra-red spectroscopy reveals competitive water and dinitrogen coordination to a manganese(i) carbonyl complex
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Ligand-based electronic effects on the electrocatalytic hydrogen production by thiosemicarbazone nickel complexes
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Regioselectivity of hyoscyamine 6β-hydroxylase-catalysed hydroxylation as revealed by high-resolution structural information and QM/MM calculations
From the themed collection: Inorganic Reaction Mechanisms
Paper

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 C[double bond, length as m-dash]C epoxidation mechanisms of the enzymes by a high-valent iron(IV)–oxo intermediate.

Graphical abstract: Computational studies of DNA base repair mechanisms by nonheme iron dioxygenases: selective epoxidation and hydroxylation pathways
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound
From the themed collection: Inorganic Reaction Mechanisms
Paper

Spin state and reactivity of iron(IV)oxido complexes with tetradentate bispidine ligands

The iron(IV)oxido complex [(bispidine)FeIV[double bond, length as m-dash]O(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.

Graphical abstract: Spin state and reactivity of iron(iv)oxido complexes with tetradentate bispidine ligands
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Peroxocobalt(iii) species activates nitriles via a superoxocobalt(ii) diradical state
From the themed collection: Inorganic Reaction Mechanisms
Paper

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).

Graphical abstract: Steric and electronic effects on acetate-assisted cyclometallation of 2-phenylpyridines at [MCl2Cp*]2 (M = Ir, Rh)
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Discovery and mechanistic investigation of Pt-catalyzed oxidative homocoupling of benzene with PhI(OAc)2
From the themed collection: Inorganic Reaction Mechanisms
Open Access Paper

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.

Graphical abstract: Routes of iron entry into, and exit from, the catalytic ferroxidase sites of the prokaryotic ferritin SynFtn
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: 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
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Tandem deoxygenative hydrosilation of carbon dioxide with a cationic scandium hydridoborate and B(C6F5)3
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Base-controlled mechanistic divergence between iron(iv)-oxo and iron(iii)-hydroperoxo in the H2O2 activation by a nonheme iron(ii) complex
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Reactivity patterns of vanadium(iv/v)-oxo complexes with olefins in the presence of peroxides: a computational study
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: Proton-assisted air oxidation mechanisms of iron(ii) bis-thiosemicarbazone complexes at physiological pH: a kinetico-mechanistic study
From the themed collection: Inorganic Reaction Mechanisms
Paper

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.

Graphical abstract: On the reaction mechanism of an endoperoxide ring formation by fumitremorgin B endoperoxidase. The right arrangement makes a difference
From the themed collection: Inorganic Reaction Mechanisms
Open Access Paper

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.

Graphical abstract: 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
From the themed collection: Inorganic Reaction Mechanisms
25 items

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.

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