Themed collection Challenges in organometallic & coordination chemistry: in celebration of Geoff Cloke’s 65th birthday

Homoleptic arenemetalates, including the depicted [K(18-crown-6)]₂[Hf(C₁₄H₁₀)₃], are often useful sources of “naked” metal anions and have been obtained for several transition metals via the Chatt reaction, named in honor of Joseph Chatt, a giant of chemistry.

Challenges and opportunities in the synthesis of pentalenide complexes are reviewed from a practical point of view.

This perspective highlights the effects of O-donor fluorinated ligands on Cu–O₂ chemistry, with intermediates capable of substrate oxidation reactivity.

Block copolymers containing polyolefin (red) and polar (blue) segments may be synthesised via end-functionalised polyolefins from metal-catalysed routes.

A series of reduced PDI neodymium complexes by the PDI ligand acting as an electron sink.

Phosphines react with the benzisothiazolinate (bit) paddlewheel dimer, [Ni₂(μ-bit)₄·2H₂O], resulting in sulfur–nitrogen bond scission and a series of unexpected transformations leading to novel Ni(II) complexes containing 2-cyanophenylthiolate and related thiolate ligands.

Coordinating rare earth ions to bis(dithiooxalato)nickel produces the first structurally characterised complexes possessing the elusive dithiooxalato radical ligand.

We report an alternative, improved, multigram scale (∼20 g, 60–70% yield) preparation of solvent-free anhydrous Li[BAr^F₄], Na[BAr^F₄] and K[BAr^F₄], and the corresponding single-crystal X-ray characterisation of [Li(H₂O)][BAr^F₄], Na[BAr^F₄]˙ and K[BAr^F₄].

Heating Pd(OAc)₂ with ortho-biphenylphosphine ligands in alcoholic solvents gives facile P–C bond-cleavage, yielding Pd(I)-dimers bridged by phosphide ligands.

AsCl₃ and AsBr₃ are shown to undergo oxidative addition to Pt(0) complexes. With AsCl₃, a single As–Cl oxidative addition step selectively yields (chloro)(arsenido)-Pt(II) complexes, whereas with AsBr₃ both monomeric and cluster compounds are produced.

A new entry point into the organometallic chemistry of reactive rhodium(I) pincer complexes.

The air stable and high yielding tetranuclear coordination cluster [Cu^II₂Dy^III₂L₄(NO₃)₂(CH₃CN)₂]·2(CH₃CN) promotes the Suzuki coupling reaction of phenylboronic acid with substituted aryl halides under environmentally benign conditions.

Reactions of a diboranate with organic nitriles result in B–C bond formation and variable behaviour that is rationalised as due to substituent-dependent modulation in the basicity and electrophilicity of Mg-coordinated nitrile intermediates.

Iron–sulfur clusters are exceptionally tuneable protein cofactors, and as one of their many roles they are involved in biological responses to nitrosative stress.

This work provides new routes for the conversion of U(IV) into U(VI) bis(imido) complexes and offers new information on the manner in which the U(VI) compounds form.

Theoretical and experimental examination of the bonding situation in uranium complexes bearing terminal hydrochalcogenido and chalcogenido ligands.

The zerovalent carbodiphosphorane, (Ph₃P)₂C, reacts with Me₃Al and Me₃Ga to afford the adducts, [(Ph₃P)₂C]MMe₃ (M = Al, Ga), whereas Me₂Zn and Me₂Mg react to afford mononuclear and dinuclear cyclometalated derivatives.

A series of cyaphide–alkynyl complexes exhibits significant cooperativity between the electron accepting “–CP” ligand and remote alkynyl substituents, indicative of long-range communication.

Anilido-imino-based ligands have been used to generate new zinc complexes, including rare zinc phosphanide and phosphinodichalcogenoate complexes. The fluorescence intensity of these compounds is highly dependent upon the non-ancillary ligand.

Cooperative catalytic hydroamination of diphenylacetylene and styrene is accomplished by magnesiates with efficiency dependent on the alkali metal and monoanionic or dianionic nature of the ate with dianionic [(PMDETA)₂K₂Mg(CH₂SiMe₃)₄] performing best.

The first REMPI/DFT study of a mixed sandwich complex reveals fine ligand effects on structural transformations accompanying electronic excitation.

Exploring the balance of energetics between planar and pyramidal forms of [Y(O-2,6-^tBu₂-4-MePh)₃] and related complexes.

Low-coordinate dinuclear lanthanide complexes supported by siloxides effect the reduction of carbon dioxide to both carbonate and oxalate, but the cooperative binding of CO2 to the two Ln(II) cations in the dimer favours oxalate formation.

Two new organometallic cyclooctatetraenyl complexes of the type [M₂(COT)₃(THF)₂] (M = Y and La) have been prepared, using optimized synthetic procedures, and fully characterized by X-ray diffraction analysis, IR and ¹H NMR spectroscopies.

Reaction of molecular O₂ with thorium alkyl complexes supported by amidinates and guanidinates generates thorium alkoxides via O₂ insertion into thorium-carbon bonds.

The boroxide ligand [OBAr₂]⁻ (Ar = Mes, Trip) is shown to be able to support both U^III and U^IV centres for the first time.

Tri- and tetranuclear macrocyclic zinc alkoxides act as catalysts for the ring-opening polymerisation of epoxides and carbon dioxide.

Anti-bimetallic transition metal complexes based on the permethylpentanyl ligand: anti-(MCp^R₅)₂Pn* (M = Fe, Co and Ni) have been synthesised and fully characterised.

Insertion reactions of N,N′-dialkyl and N,N′-diaryl carbodiimides with a dimeric calcium hydride provide formamidinate derivatives whose structures on the steric demands of the carbodiimide reagent.

Addition of ZnMe₂ to cationic and neutral ruthenium hydride complexes bearing NHC ligands affords new Ru–Zn heterobimetallic complexes.

A series of Group 2 and 12 heteroscorpionate complexes is reported.

Redox switchable catalysis with a ferrocene Schiff base zirconium complex allowed the synthesis of diblock and triblock copolymers.

The structure of a di(amino)stibine has been determined by neutron diffraction giving the first accurate parameters for the Sb^III–H bond.

Trends in covalency of structurally analogous d and f element compounds are explored over changes in the M–O bond distance.

We report that crystallographically-characterizable Ln(II) complexes of Tb and Ho can be isolated by reducing Cp^Me₃Ln(THF) with KC₈ in THF in the presence of 18-crown-6 (18-c-6).

Selective sensing of glyphosate in the micromolar regime in water.