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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Syntheses and electronic structures of μ-nitrido bridged pyridine, diimine iridium complexes
Oxidation states in late transition metal nitrido complexes.
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.
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.
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.
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.
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.