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Themed collection Non-Innocent Ligands

17 articles
Editorial

Non-innocent ligands

Guest editors Louise Berben, Bas de Bruin and Alan Heyduk introduce this web collection focusing on recent achievements within the field of non-innocent ligands.

Graphical abstract: Non-innocent ligands
From the themed collection: Non-Innocent Ligands
Feature Article

Metal–ligand bifunctional reactivity and catalysis of protic N-heterocyclic carbene and pyrazole complexes featuring β-NH units

The metal–ligand bifunctional cooperation of protic N-heterocyclic carbene and pyrazole complexes bearing an NH unit at the position β to the metal is surveyed.

Graphical abstract: Metal–ligand bifunctional reactivity and catalysis of protic N-heterocyclic carbene and pyrazole complexes featuring β-NH units
From the themed collection: Non-Innocent Ligands
Open Access Feature Article

Organic azides: “energetic reagents” for the intermolecular amination of C–H bonds

This feature article highlights the potentiality of organic azides (RN3) for the intermolecular amination of sp3 and sp2 C–H bonds. A compendium of employed catalytic systems, together with a discussion of involved mechanisms, is provided.

Graphical abstract: Organic azides: “energetic reagents” for the intermolecular amination of C–H bonds
From the themed collection: Non-Innocent Ligands
Communication

Classical and non-classical redox reactions of Pd(II) complexes containing redox-active ligands

Chemical reactions of a verdazyl radical–palladium complex reveal the verdazyl’s functionality as a redox-active ligand and a “cooperative” (acido-basic) ligand.

Graphical abstract: Classical and non-classical redox reactions of Pd(ii) complexes containing redox-active ligands
From the themed collection: Non-Innocent Ligands
Communication

Geometric and redox flexibility of pyridine as a redox-active ligand that can reversibly accept one or two electrons

A low-coordinate iron(I) species can reversibly reduce pyridine by one or two electrons, through changes in C–C bonding.

Graphical abstract: Geometric and redox flexibility of pyridine as a redox-active ligand that can reversibly accept one or two electrons
From the themed collection: Non-Innocent Ligands
Open Access Communication

Platinum corroles

Platinum has been inserted into corroles for the first time and three oxidized PtIV(corrole˙2−)ArAr′ complexes have been structurally characterized.

Graphical abstract: Platinum corroles
From the themed collection: Non-Innocent Ligands
Open Access Communication

(Electro)catalytic C–C bond formation reaction with a redox-active cobalt complex

Cooperativity between cobalt and non-innocent ligands in electron transfer processes has been utilized for (electro)catalytic C–C bond formation reactions.

Graphical abstract: (Electro)catalytic C–C bond formation reaction with a redox-active cobalt complex
From the themed collection: Non-Innocent Ligands
Open Access Communication

An electron transfer series of octahedral chromium complexes containing a redox non-innocent α-diimine ligand

An electron-transfer series of octahedral α-diimine complexes [(HLCy)3Cr]n+(BARF)n (n = 2, 1, 0) has been synthesized and crystallographically characterized.

Graphical abstract: An electron transfer series of octahedral chromium complexes containing a redox non-innocent α-diimine ligand
From the themed collection: Non-Innocent Ligands
Communication

Iminosemiquinone radical ligands enable access to a well-defined redox-active CuII–CF3 complex

The reaction of a copper complex bearing iminosemiquinone ligands with a CF3+ source provides an unprecedented CuII–CF3 complex through ligand-based oxidation.

Graphical abstract: Iminosemiquinone radical ligands enable access to a well-defined redox-active CuII–CF3 complex
From the themed collection: Non-Innocent Ligands
Communication

Adaptive behavior of a redox-active gallium carbenoid in complexes with molybdenum

A gallium–nitrogen heterocycle derived from 1,2-bis(imino)acenaphthene may serve either as a neutral or an anionic two-electron donor depending on the electronic state of the transition metal.

Graphical abstract: Adaptive behavior of a redox-active gallium carbenoid in complexes with molybdenum
From the themed collection: Non-Innocent Ligands
Communication

Influence of redox non-innocent phenylenediamido ligands on chromium imido hydrogen-atom abstraction reactivity

Reaction of new CpCr[(RN)2C6H4] complexes (R = SiMe3, CH2CMe3, Ph) with organic azides generates chromium imido complexes.

Graphical abstract: Influence of redox non-innocent phenylenediamido ligands on chromium imido hydrogen-atom abstraction reactivity
From the themed collection: Non-Innocent Ligands
Open Access Communication

Evidence of two-state reactivity in alkane hydroxylation by Lewis-acid bound copper–nitrene complexes

Two state reactivity hypothesis, well established for iron-oxo cores, can also be extended to the copper–nitrenes.

Graphical abstract: Evidence of two-state reactivity in alkane hydroxylation by Lewis-acid bound copper–nitrene complexes
From the themed collection: Non-Innocent Ligands
Communication

Syntheses and electronic structures of μ-nitrido bridged pyridine, diimine iridium complexes

Oxidation states in late transition metal nitrido complexes.

Graphical abstract: Syntheses and electronic structures of μ-nitrido bridged pyridine, diimine iridium complexes
From the themed collection: Non-Innocent Ligands
Open Access Communication

Mechanistic investigation of the selective reduction of Meldrum's acids to β-hydroxy acids using SmI2 and H2O

The mechanism of the mono-reduction of Meldrum's acids to β-hydroxy acids employing SmI2–H2O has been elucidated.

Graphical abstract: Mechanistic investigation of the selective reduction of Meldrum's acids to β-hydroxy acids using SmI2 and H2O
From the themed collection: Non-Innocent Ligands
Communication

Utility of a redox-active pyridine(diimine) chelate in facilitating two electron oxidative addition chemistry at uranium

Tetravalent CpPU(MesPDIMe) uses its [MesPDIMe]3− chelate to perform oxidative addition of halides and dichalcogenides, generating the uranium(IV) family, CpPU(XX′)(MesPDIMe) (X = X′ = I; X = X′ = Cl; X = SePh, X′ = Cl; X = X′ = EPh), which is supported by [MesPDIMe]1− ligand.

Graphical abstract: Utility of a redox-active pyridine(diimine) chelate in facilitating two electron oxidative addition chemistry at uranium
From the themed collection: Non-Innocent Ligands
Communication

Octahedral to trigonal prismatic distortion driven by subjacent orbital π antibonding interactions and modulated by ligand redox noninnocence

Ruthenium and osmium bis(amidodiphenoxides) distort towards trigonal prismatic geometries to minimize aryloxide-to-metal π* interactions, limited by increasing degree of oxidation of the redox-active ligand.

Graphical abstract: Octahedral to trigonal prismatic distortion driven by subjacent orbital π antibonding interactions and modulated by ligand redox noninnocence
From the themed collection: Non-Innocent Ligands
Open Access Communication

Synthesis and ligand-based reduction chemistry of boron difluoride complexes with redox-active formazanate ligands

Mono(formazanate) boron difluoride complexes (LBF2), which show remarkably facile and reversible ligand-based redox-chemistry, were synthesized by transmetallation of bis(formazanate) zinc complexes with boron trifluoride.

Graphical abstract: Synthesis and ligand-based reduction chemistry of boron difluoride complexes with redox-active formazanate ligands
From the themed collection: Non-Innocent Ligands
17 articles

About this collection

This ChemComm themed collection publishes contributions from all areas of chemistry that include the use of ligands that are both redox non-innocent and chemically non-innocent. It covers not only synthetic inorganic chemistry and catalysis, but also other applications of non-innocent ligand chemistry. The issue is Guest Edited by Louise Berben, Alan Heyduk and Bas de Bruin. New articles will be added to this collection as they are published.

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