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Themed collection Mechanistic Organometallic Chemistry

17 articles
Cover

Front cover

Graphical abstract: Front cover
From the themed collection: Mechanistic Organometallic Chemistry
Cover

Inside front cover

Graphical abstract: Inside front cover
From the themed collection: Mechanistic Organometallic Chemistry
Editorial

How far have we come?

Welcome to this Dalton Transactions themed issue on Mechanistic organometallic chemistry.

Graphical abstract: How far have we come?
From the themed collection: Mechanistic Organometallic Chemistry
Communication

Deuteration of boranes: catalysed versus non-catalysed processes

Borane and alkylboranes can undergo deuteration in the absence of a catalyst, while pincolborane and catchecol borane cannot; an iridium complex is shown to catalyse the deuteration of the latter compounds.

Graphical abstract: Deuteration of boranes: catalysed versus non-catalysed processes
From the themed collection: Mechanistic Organometallic Chemistry
Communication

Solvent effects on Grubbs’ pre-catalyst initiation rates

Initiation rates for Grubbs and Grubbs–Hoveyda second generation pre-catalysts have been measured accurately in a range of solvents. No simple correlations to single solvent properties were discovered; instead, a multi-parameter approach was necessary to correctly treat the experimental data.

Graphical abstract: Solvent effects on Grubbs’ pre-catalyst initiation rates
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Computational study on mechanism of Rh(III)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes

A mechanistic study on the Rh(III)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes has been performed with DFT calculations.

Graphical abstract: Computational study on mechanism of Rh(iii)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Ethylene polymerisation and oligomerisation with arene-substituted phenoxy-imine complexes of titanium: investigation of multi-mechanism catalytic behaviour

A range of arene-substituted phenoxy-imine complexes of Ti(IV) have been prepared and evaluated in ethylene oligomerisation and polymerisation.

Graphical abstract: Ethylene polymerisation and oligomerisation with arene-substituted phenoxy-imine complexes of titanium: investigation of multi-mechanism catalytic behaviour
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Understanding intermolecular C–F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2 + 2]-cycloaddition/β-fluoride elimination

The mechanisms to C–F bond activation of fluoropyridines by a transient titanium alkylidyne are presented.

Graphical abstract: Understanding intermolecular C–F bond activation by a transient titanium neopentylidyne: experimental and theoretical studies on the competition between 1,2-CF bond addition and [2 + 2]-cycloaddition/β-fluoride elimination
From the themed collection: Mechanistic Organometallic Chemistry
Paper

C–N coupling in the gas-phase reactions of ammonia and [M(CH)]+ (M = Ni, Pd, Pt): a combined experimental/computational exercise

Electrospray ionization of methanolic solutions of monomeric nickel(II) acetate and tetrameric platinum(II) acetate leads to the formation of the corresponding methylidyne complexes [M(CH)]+ (M = Ni, Pt), which react with ammonia under C–N coupling.

Graphical abstract: C–N coupling in the gas-phase reactions of ammonia and [M(CH)]+ (M = Ni, Pd, Pt): a combined experimental/computational exercise
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: an experimental and theoretical study

Two diazo compounds can be coupled to form an olefin in a reaction catalyzed by copper and silver complexes.

Graphical abstract: Catalytic cross-coupling of diazo compounds with coinage metal-based catalysts: an experimental and theoretical study
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Accelerating Ni(II) precatalyst initiation using reactive ligands and its impact on chain-growth polymerizations

Initiation rates were selectively accelerated in Ni-catalyzed chain-growth polymerizations using aryl-functionalized precatalysts.

Graphical abstract: Accelerating Ni(ii) precatalyst initiation using reactive ligands and its impact on chain-growth polymerizations
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Computational study of the double C–Cl bond activation of dichloromethane and phosphine alkylation at [CoCl(PR3)3]

The double C–Cl activation of CH2Cl2 at [CoCl(PMe3)3] has been modelled with DFT calculations.

Graphical abstract: Computational study of the double C–Cl bond activation of dichloromethane and phosphine alkylation at [CoCl(PR3)3]
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Radical-chain oxidative addition mechanism for the reaction of an [Re(CO)5] anion with α-bromostilbene

An oxidative addition reaction of α-bromostilbene to Na[Re(CO)5] carbonylmetallate is shown to proceed by a radical-chain mechanism involving a 17-electron [Re(CO)4{C(Ph)[double bond, length as m-dash]CHPh}]˙ radical-anion intermediate.

Graphical abstract: Radical-chain oxidative addition mechanism for the reaction of an [Re(CO)5]− anion with α-bromostilbene
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane

RhIII species were found to be the active species involved in the formation of long polymers in the Rh-mediated carbene polymerisation of diazomethane, while RhI species are involved in the formation of short oligomers and dimers.

Graphical abstract: Propagation and termination steps in Rh-mediated carbene polymerisation using diazomethane
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Platinum(II) and platinum(IV) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes

C4-bound imidazolylidene-type dicarbene ligands bound to platinum(II) centers induce solvolysis of the metal-bound halide and facile oxidative addition to yield stable platinum(IV) complexes.

Graphical abstract: Platinum(ii) and platinum(iv) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes
From the themed collection: Mechanistic Organometallic Chemistry
Paper

Computational Hammett analysis of redox based oxy-insertion by Pt(II) complexes

A computational Hammett study is performed comparing non-redox and redox mechanisms for late transition metal mediated carbon–oxygen bond formation.

Graphical abstract: Computational Hammett analysis of redox based oxy-insertion by Pt(ii) complexes
From the themed collection: Mechanistic Organometallic Chemistry
Paper

A combined NMR/DFT study on the ion pair structure of [(PR12R2)Au(η2-3-hexyne)]BF4 complexes

The effect of the electronic properties of a P-ligand on the ion pair structure of the catalytically relevant [(PR12R2)Au(η2-3-hexyne)]BF4 ion pairs has been investigated by combining 19F, 1H-HOESY NMR and relativistic DFT calculations.

Graphical abstract: A combined NMR/DFT study on the ion pair structure of [(PR12R2)Au(η2-3-hexyne)]BF4 complexes
From the themed collection: Mechanistic Organometallic Chemistry
17 articles

About this collection

This themed issue, guest edited by Professor Bob Crabtree, aims to highlight the importance of mechanism to the field of organometallic chemistry. Read below for a selection of both theoretical and experimental research contributions, providing deeper insight into current problems.

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