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Themed collection Reactions Facilitated by Ligand Design

37 items
Editorial

Reactions facilitated by ligand design

Welcome to this themed issue of Dalton Transactions entitled “Reactions facilitated by ligand design”.

Graphical abstract: Reactions facilitated by ligand design
From the themed collection: Reactions Facilitated by Ligand Design
Perspective

Metal–ligand cooperation at tethered π-ligands

Recent advances in the use of tethered π-coordinating ligands for metal–ligand cooperation.

Graphical abstract: Metal–ligand cooperation at tethered π-ligands
From the themed collection: Reactions Facilitated by Ligand Design
Perspective

Group 5 chemistry supported by β-diketiminate ligands

β-Diketiminate (BDI) ligands are widely used supporting ligands in modern organometallic chemistry and are capable of stabilizing various metal complexes in multiple oxidation states and coordination environments.

Graphical abstract: Group 5 chemistry supported by β-diketiminate ligands
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Perspective

The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts

This Perspective illustrates the state-of-the-art of stereoselective carbene transfer reactions catalysed by chiral metal porphyrin complexes. A particular attention is focused on the active role of the porphyrin ligand to drive the carbene insertion into the target organic skeleton.

Graphical abstract: The ligand influence in stereoselective carbene transfer reactions promoted by chiral metal porphyrin catalysts
From the themed collection: Reactions Facilitated by Ligand Design
Perspective

Current advances in ligand design for inorganic positron emission tomography tracers 68Ga, 64Cu, 89Zr and 44Sc

A key part of the development of metal based Positron Emission Tomography probes is the chelation of the radiometal.

Graphical abstract: Current advances in ligand design for inorganic positron emission tomography tracers 68Ga, 64Cu, 89Zr and 44Sc
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Communication

Boosting catalyst activity in cis-selective semi-reduction of internal alkynes by tailoring the assembly of all-metal aromatic tri-palladium complexes

Zwitterionic all-metal aromatic tri-palladium complexes can catalyse the cis-selective semi-reduction of internal alkynes at ppm levels.

Graphical abstract: Boosting catalyst activity in cis-selective semi-reduction of internal alkynes by tailoring the assembly of all-metal aromatic tri-palladium complexes
From the themed collection: Reactions Facilitated by Ligand Design
Communication

Carbon dioxide cleavage across a tungsten-alkylidyne bearing a trianionic pincer-type ligand

Splitting of CO2 across the tungsten-carbon triple bond in [CF3-ONO]W[triple bond, length as m-dash]CCtBu(THF)2 (1) yields the tungsten oxo ketene [CF3-ONO]W(O){(CH3)3CC[double bond, length as m-dash]C[double bond, length as m-dash]O} (6).

Graphical abstract: Carbon dioxide cleavage across a tungsten-alkylidyne bearing a trianionic pincer-type ligand
From the themed collection: Reactions Facilitated by Ligand Design
Communication

A multimetallic iron(II)–lithium complex as a catalyst for ε-caprolactone polymerization

Treatment of the lithium salt of β-ketimine with FeCl2(THF)1.5 in the presence of LiN(SiMe3)2 and water affords the multimetallic iron(II)–lithium complex 1, [(LMe)2Fe]3Li2O [where LMe = MeC(O)CHC(NMe)Me].

Graphical abstract: A multimetallic iron(ii)–lithium complex as a catalyst for ε-caprolactone polymerization
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Copper catalysed aerobic oxidation of benzylic alcohols in an imidazole containing N4 ligand framework

The catalytic aerobic oxidation of benzylic alcohols to corresponding aldehydes has been investigated employing a tetradentate copper(II) complex that incorporates N-methyl imidazole (NMI) as an integral part of an N4-ligand framework.

Graphical abstract: Copper catalysed aerobic oxidation of benzylic alcohols in an imidazole containing N4 ligand framework
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands

The unusual situation presented by a silicon centre coordinating four 1,3-dipolar ligands is exploited in thermally activated cycloaddition reactions with nitriles that lead to six-coordinate poly(tetrazolato) complexes of silicon.

Graphical abstract: Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

Dinuclear uranium complexation and manipulation using robust tetraaryloxides

Two lower-oxidation state uranium cations can be readily combined and controlled in a robust and derivatisable tetra-aryloxide ligand framework. These di-UIII/IV systems are a new platform at which to use the multi-electron reductive capacity of the two actinide centres.

Graphical abstract: Dinuclear uranium complexation and manipulation using robust tetraaryloxides
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

Metal–ligand cooperative activation of nitriles by a de-aromatized Ru pincer complex leads to equilibrium mixtures (tautomers) as a result of ligand deprotonation by the Brønsted basic Ru-ketimido moiety.

Graphical abstract: Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Coordination versatility of p-hydroquinone-functionalized dibenzobarrelene-based PC(sp3)P pincer ligands

Bifunctional hydroquinone-based PC(sp3)P pincer complexes.

Graphical abstract: Coordination versatility of p-hydroquinone-functionalized dibenzobarrelene-based PC(sp3)P pincer ligands
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Synthesis of a sterically bulky diphosphine synthon and Ru(II) complexes of a cooperative tridentate enamide-diphosphine ligand platform

The preparation of the bulky diphosphine synthon 1 is described and used to generate a tridentate enamido diphosphine ligand platform that can be installed on Ru(II).

Graphical abstract: Synthesis of a sterically bulky diphosphine synthon and Ru(ii) complexes of a cooperative tridentate enamide-diphosphine ligand platform
From the themed collection: Reactions Facilitated by Ligand Design
Paper

The control of the electronic structure of dinuclear copper complexes of redox-active tetrakisguanidine ligands by the environment

The electronic structures of dinuclear copper complexes of the general formula [GFA(CuX2)2], where X = Br or Cl and GFA denotes a redox-active bridging Guanidino-Functionalized Aromatic ligand, were analysed and compared.

Graphical abstract: The control of the electronic structure of dinuclear copper complexes of redox-active tetrakisguanidine ligands by the environment
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

Changing the chemical and physical properties of high valent heterobimetallic bis-(μ-oxido) Cu–Ni complexes by ligand effects

Two new heterobimetallic [LNiO2Cu(RPY2)]+ (RPY2 = N-substituted bis 2-pyridyl(ethylamine) ligands with R = indane, 3a or R = Me, 3b) complexes have been spectroscopically trapped at low temperatures.

Graphical abstract: Changing the chemical and physical properties of high valent heterobimetallic bis-(μ-oxido) Cu–Ni complexes by ligand effects
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Bimetallic salen aluminum complexes: cooperation between reactive centers in the ring-opening polymerization of lactides and epoxides

In dinuclear aluminum complexes, opportunely designed to have proximal coordinative pockets, the communication between the two reactive centers allows enhanced catalytic performances.

Graphical abstract: Bimetallic salen aluminum complexes: cooperation between reactive centers in the ring-opening polymerization of lactides and epoxides
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Chelating N-heterocyclic carbene–carboranes offer flexible ligand coordination to IrIII, RhIII and RuII: effect of ligand cyclometallation in catalytic transfer hydrogenation

NHC–carborane ligands, with flexible coordination through either the carbon or the boron atom of the carborane, provide effective transfer hydrogenation catalysts.

Graphical abstract: Chelating N-heterocyclic carbene–carboranes offer flexible ligand coordination to IrIII, RhIII and RuII: effect of ligand cyclometallation in catalytic transfer hydrogenation
From the themed collection: Reactions Facilitated by Ligand Design
Paper

On the mechanism of Ni(II)-promoted Michael-type hydroamination of acrylonitrile and its substituted derivatives

Monocationic Ni(II) complexes featuring variously substituted POCOP-type pincer ligands promote the addition of primary amines to crotonitrile, methacrylonitrile, and cinnamonitrile.

Graphical abstract: On the mechanism of Ni(ii)-promoted Michael-type hydroamination of acrylonitrile and its substituted derivatives
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

RuII, IrIII and OsII mesoionic carbene complexes: efficient catalysts for transfer hydrogenation of selected functionalities

Pyridine- and pyrimidine-appended triazolylidene donors are used as ligands for the transfer hydrogenation of a series of functionalities.

Graphical abstract: RuII, IrIII and OsII mesoionic carbene complexes: efficient catalysts for transfer hydrogenation of selected functionalities
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO2 using supramolecular assembly

The use of hydrogen-bonding interactions to direct the non-covalent assembly of a heterobimetallic supramolecular system with Re and Mn bipyridine-based electrocatalysts is reported.

Graphical abstract: Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO2 using supramolecular assembly
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Aluminum complexes containing biphenolate phosphine ligands: synthesis and living ring-opening polymerization catalysis

The first examples of aluminum complexes containing biphenolate phosphine ligands are prepared, structurally characterized, and demonstrated to have catalytic competence in the living ring-opening (co)polymerization of ε-caprolactone and rac-lactide.

Graphical abstract: Aluminum complexes containing biphenolate phosphine ligands: synthesis and living ring-opening polymerization catalysis
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

An electron poor iridium pincer complex for catalytic alkane dehydrogenation

A new electron deficient iridium complex demonstrates an improved TON in alkane transfer dehydrogenation reactions compared to similar pre-catalysts.

Graphical abstract: An electron poor iridium pincer complex for catalytic alkane dehydrogenation
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Thermodynamics of N–H bond formation in bis(phosphine) molybdenum(II) diazenides and the influence of the trans ligand

Dinitrogen-derived molybdenum alkyldiazenides and alkylhydrazides were synthesized with various trans ligands. The thermodynamics of N–H bond formation were studied both experimentally and computationally.

Graphical abstract: Thermodynamics of N–H bond formation in bis(phosphine) molybdenum(ii) diazenides and the influence of the trans ligand
Open Access Paper

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

Interactions between the uranyl oxo atom and group 14 metal cations in macrocyclic Pacman complexes depend on both molecular cleft constraints and the fifth equatorial ligand of the uranyl.

Graphical abstract: Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Relativistic DFT and experimental studies of mono- and bis-actinyl complexes of an expanded Schiff-base polypyrrole macrocycle

Relativistic DFT calculations present accurate geometries of complexes and redox properties, confirmed by the newly-developed experimental syntheses.

Graphical abstract: Relativistic DFT and experimental studies of mono- and bis-actinyl complexes of an expanded Schiff-base polypyrrole macrocycle
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Theoretical investigation of low-valent uranium and transuranium complexes of a flexible small-cavity macrocycle: structural, formation reaction and redox properties

Size matching of a flexible macrocycle with low-valent actinide(III/IV) ions as well as their bonding determines different coordination modes.

Graphical abstract: Theoretical investigation of low-valent uranium and transuranium complexes of a flexible small-cavity macrocycle: structural, formation reaction and redox properties
From the themed collection: Reactions Facilitated by Ligand Design
Paper

A long-tethered (P–B–P)-pincer ligand: synthesis, complexation, and application to catalytic dehydrogenation of alkanes

A new long-tethered boron-containing (P–B–P)-pincer ligand has been synthesized. This ligand was introduced to Ir to form (P–B–P)Ir(H)Cl complex. Subsequent reaction with nBuLi led to the formation of dihydride complex (P–B–P)Ir(H)2. Both complexes were found to be moderately active for the catalytic dehydrogenation of alkanes.

Graphical abstract: A long-tethered (P–B–P)-pincer ligand: synthesis, complexation, and application to catalytic dehydrogenation of alkanes
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Synthesis and reactions of a zirconium naphthalene complex bearing a tetraanionic C-capped triaryloxide ligand

A zirconium naphthalene complex containing a C-capped triaryloxide ligand, which can act as a Zr(II) synthon, was synthesized and fully characterized.

Graphical abstract: Synthesis and reactions of a zirconium naphthalene complex bearing a tetraanionic C-capped triaryloxide ligand
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Reversible methanol addition to copper Schiff base complexes: a kinetic, structural and spectroscopic study of reactions at azomethine C[double bond, length as m-dash]N bonds

The reversible ligand-directed methanolysis of a series of copper(II) Schiff base complexes reveal slightly favorable equilibrium constants with addition and eliminations rates influenced by the identity of the axial ligand.

Graphical abstract: Reversible methanol addition to copper Schiff base complexes: a kinetic, structural and spectroscopic study of reactions at azomethine C [[double bond, length as m-dash]] N bonds
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

The influence of the ligand chelate effect on iron-amine-catalysed Kumada cross-coupling

The performance of Fe-amine pre-catalysts in a representative Kumada reaction is inversely proportional to the lability of the chelate ligand.

Graphical abstract: The influence of the ligand chelate effect on iron-amine-catalysed Kumada cross-coupling
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Ligand effects on the properties of Ni(III) complexes: aerobically-induced aromatic cyanation at room temperature

Ligand effect studies on (RN3C)NiIIIL2 complexes reveal aerobically-induced aromatic cyanation with tBuNC at room temperature for the (NpN3C)Ni system.

Graphical abstract: Ligand effects on the properties of Ni(iii) complexes: aerobically-induced aromatic cyanation at room temperature
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Unexpected reactivity of an alkylaluminum complex of a non-innocent 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian)

The non-innocence of the bis-amido dpp-bian ligand has been documented by the reactions of compound 1 with acidic substrates, e.g. water.

Graphical abstract: Unexpected reactivity of an alkylaluminum complex of a non-innocent 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene ligand (dpp-bian)
From the themed collection: Reactions Facilitated by Ligand Design
Paper

Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex

The synthesis and characterization of a terminal titanium oxo complex generated by alkylidene benzophenone cross-metathesis is reported.

Graphical abstract: Metallo-Wittig chemistry of an alkylidene to form a terminal titanium oxo complex
Paper

Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation

New electronically and coordinatively unsaturated complexes of the type (Cy-PSiP)RuX(L) (Cy-PSiP = κ3-(2-Cy2PC6H4)2SiMe) are reported, including examples of 16-electron allyl and azido Ru species.

Graphical abstract: Synthesis and characterization of five-coordinate, 16-electron RuII complexes supported by tridentate bis(phosphino)silyl ligation
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

Versatile bonding and coordination modes of ditriazolylidene ligands in rhodium(III) and iridium(III) complexes

Metalation of novel ditriazolium salts containing a trimethylene (–CH2CH2CH2–) or dimethylether linker (–CH2OCH2–) was probed with different rhodium(III) and iridium(III) precursors.

Graphical abstract: Versatile bonding and coordination modes of ditriazolylidene ligands in rhodium(iii) and iridium(iii) complexes
From the themed collection: Reactions Facilitated by Ligand Design
Open Access Paper

Iron(II) β-ketiminate complexes as mediators of controlled radical polymerisation

A series of novel iron(II) β-ketiminate complexes have been prepared and screened in styrene and methyl methacrylate CRP.

Graphical abstract: Iron(ii) β-ketiminate complexes as mediators of controlled radical polymerisation
From the themed collection: Reactions Facilitated by Ligand Design
37 items

About this collection

This issue focusses on transformations involving inorganic complexes where a ligand design approach has been used to produce a demonstrable change in reactivity. The collection includes papers across  inorganic or organometallic chemistry, including catalysis, small molecule activation, C–X bond activation, bioinorganic chemistry and supramolecular chemistry. Ligand classes include pincers, carbenes, macrocyclic ligands, phosphines or metallocenes, and approaches for goal-oriented ligand design involving aspects such as redox non-innocence, steric hindrance, secondary coordination sphere effects and manipulation of Lewis pairs.

Spotlight

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