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

34 items
Open Access Perspective

Synthesis of organometallic pentalenide complexes

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

Graphical abstract: Synthesis of organometallic pentalenide complexes
From the themed collection: Dalton Transactions HOT Articles
Perspective

Cu(I)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment

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

Graphical abstract: Cu(i)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment
From the themed collection: 2019 Frontier and Perspective articles
Perspective

End-functional polyolefins for block copolymer synthesis

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

Graphical abstract: End-functional polyolefins for block copolymer synthesis
From the themed collection: Dalton Transactions HOT Articles
Perspective

The Chatt reaction: conventional routes to homoleptic arenemetalates of d-block elements

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.

Graphical abstract: The Chatt reaction: conventional routes to homoleptic arenemetalates of d-block elements
From the themed collection: Dalton Transactions HOT Articles
Communication

A reduction series of neodymium supported by pyridine(diimine) ligands

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

Graphical abstract: A reduction series of neodymium supported by pyridine(diimine) ligands
Communication

Phosphine-promoted ring-opening of benzisothiazolinate ligands at a nickel(II) centre: a convenient synthesis of Ni(II)-thiolate complexes

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.

Graphical abstract: Phosphine-promoted ring-opening of benzisothiazolinate ligands at a nickel(ii) centre: a convenient synthesis of Ni(ii)-thiolate complexes
Open Access Communication

Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination

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

Graphical abstract: Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination
From the themed collection: Dalton Transactions HOT Articles
Open Access Communication

Solvent-free anhydrous Li+, Na+ and K+ salts of [B(3,5-(CF3)2C6H3)4], [BArF4]. Improved synthesis and solid-state structures

We report an alternative, improved, multigram scale (∼20 g, 60–70% yield) preparation of solvent-free anhydrous Li[BArF4], Na[BArF4] and K[BArF4], and the corresponding single-crystal X-ray characterisation of [Li(H2O)][BArF4], Na[BArF4]˙ and K[BArF4].

Graphical abstract: Solvent-free anhydrous Li+, Na+ and K+ salts of [B(3,5-(CF3)2C6H3)4]−, [BArF4]−. Improved synthesis and solid-state structures
Communication

The surprisingly facile formation of Pd(I)–phosphido complexes from ortho-biphenylphosphines and palladium acetate

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.

Graphical abstract: The surprisingly facile formation of Pd(i)–phosphido complexes from ortho-biphenylphosphines and palladium acetate
From the themed collection: Dalton Transactions HOT Articles
Communication

Oxidative addition of arsenic halides to platinum(0)

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.

Graphical abstract: Oxidative addition of arsenic halides to platinum(0)
Open Access Communication

A convenient method for the generation of {Rh(PNP)}+ and {Rh(PONOP)}+ fragments: reversible formation of vinylidene derivatives

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

Graphical abstract: A convenient method for the generation of {Rh(PNP)}+ and {Rh(PONOP)}+ fragments: reversible formation of vinylidene derivatives
Communication

A tetranuclear CuII2DyIII2 coordination cluster as a Suzuki (C–C) coupling reaction promoter

The air stable and high yielding tetranuclear coordination cluster [CuII2DyIII2L4(NO3)2(CH3CN)2]·2(CH3CN) promotes the Suzuki coupling reaction of phenylboronic acid with substituted aryl halides under environmentally benign conditions.

Graphical abstract: A tetranuclear CuII2DyIII2 coordination cluster as a Suzuki (C–C) coupling reaction promoter
Paper

Reactivity of the carbodiphosphorane, (Ph3P)2C, towards main group metal alkyl compounds: coordination and cyclometalation

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.

Graphical abstract: Reactivity of the carbodiphosphorane, (Ph3P)2C, towards main group metal alkyl compounds: coordination and cyclometalation
Paper

Cyaphide–alkynyl complexes: metal–ligand conjugation and the influence of remote substituents

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

Graphical abstract: Cyaphide–alkynyl complexes: metal–ligand conjugation and the influence of remote substituents
Paper

Utilising an anilido-imino ligand to stabilise zinc-phosphanide complexes: reactivity and fluorescent properties

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.

Graphical abstract: Utilising an anilido-imino ligand to stabilise zinc-phosphanide complexes: reactivity and fluorescent properties
Paper

Alkali metal and stoichiometric effects in intermolecular hydroamination catalysed by lithium, sodium and potassium magnesiates

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.

Graphical abstract: Alkali metal and stoichiometric effects in intermolecular hydroamination catalysed by lithium, sodium and potassium magnesiates
Paper

Rydberg state mediated multiphoton ionization of (η7-C7H7)(η5-C5H5)Cr: DFT-supported experimental insights into the molecular and electronic structures of excited sandwich complexes

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

Graphical abstract: Rydberg state mediated multiphoton ionization of (η7-C7H7)(η5-C5H5)Cr: DFT-supported experimental insights into the molecular and electronic structures of excited sandwich complexes
From the themed collection: 2019 PCCP HOT Articles
Open Access Paper

Reversible temperature-induced polymorphic phase transitions of [Y(OAr)3] and [Ce(OAr)3] (Ar = 2,6-tBu2-4-MeC6H2): interconversions between pyramidal and planar geometries

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

Graphical abstract: Reversible temperature-induced polymorphic phase transitions of [Y(OAr)3] and [Ce(OAr)3] (Ar = 2,6-tBu2-4-MeC6H2): interconversions between pyramidal and planar geometries
Paper

Carbon dioxide reduction by dinuclear Yb(II) and Sm(II) complexes supported by siloxide ligands

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.

Graphical abstract: Carbon dioxide reduction by dinuclear Yb(ii) and Sm(ii) complexes supported by siloxide ligands
From the themed collection: Dalton Transactions HOT Articles
Paper

Oxidation of uranium(IV) mixed imido–amido complexes with PhEEPh and to generate uranium(VI) bis(imido) dichalcogenolates, U(NR)2(EPh)2(L)2

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.

Graphical abstract: Oxidation of uranium(iv) mixed imido–amido complexes with PhEEPh and to generate uranium(vi) bis(imido) dichalcogenolates, U(NR)2(EPh)2(L)2
Paper

Versatility of cyclooctatetraenyl ligands in rare earth metal complexes of the [M2(COT)3(THF)2] (M = Y and La) type

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.

Graphical abstract: Versatility of cyclooctatetraenyl ligands in rare earth metal complexes of the [M2(COT)3(THF)2] (M = Y and La) type
Paper

Dioxygen reacts with metal–carbon bonds in thorium dialkyls to produce bis(alkoxides)

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

Graphical abstract: Dioxygen reacts with metal–carbon bonds in thorium dialkyls to produce bis(alkoxides)
Open Access Paper

Applications of boroxide ligands in supporting small molecule activation by U(III) and U(IV) complexes

The boroxide ligand [OBAr2] (Ar = Mes, Trip) is shown to be able to support both UIII and UIV centres for the first time.

Graphical abstract: Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes
Open Access Paper

Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2

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

Graphical abstract: Polynuclear alkoxy–zinc complexes of bowl-shaped macrocycles and their use in the copolymerisation of cyclohexene oxide and CO2
Paper

A complete series of uranium(IV) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te

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

Graphical abstract: A complete series of uranium(iv) complexes with terminal hydrochalcogenido (EH) and chalcogenido (E) ligands E = O, S, Se, Te
Paper

Synthesis, characterisation and redox properties of anti-bimetallic permethylpentalene complexes

Anti-bimetallic transition metal complexes based on the permethylpentanyl ligand: anti-(MCpR5)2Pn* (M = Fe, Co and Ni) have been synthesised and fully characterised.

Graphical abstract: Synthesis, characterisation and redox properties of anti-bimetallic permethylpentalene complexes
Open Access Paper

Calcium formamidinate derivatives by hydride insertion of carbodiimides

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.

Graphical abstract: Calcium formamidinate derivatives by hydride insertion of carbodiimides
Open Access Paper

Heterobimetallic ruthenium–zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity

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

Graphical abstract: Heterobimetallic ruthenium–zinc complexes with bulky N-heterocyclic carbenes: syntheses, structures and reactivity
From the themed collection: Dalton Transactions HOT Articles
Open Access Paper

Magnesium, calcium and zinc [N2N′] heteroscorpionate complexes

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

Graphical abstract: Magnesium, calcium and zinc [N2N′] heteroscorpionate complexes
From the themed collection: Dalton Transactions HOT Articles
Paper

Investigation of a zirconium compound for redox switchable ring opening polymerization

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

Graphical abstract: Investigation of a zirconium compound for redox switchable ring opening polymerization
Paper

A study of di(amino)stibines with terminal Sb(III) hydrogen-ligands by X-ray- and neutron-diffraction

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

Graphical abstract: A study of di(amino)stibines with terminal Sb(iii) hydrogen-ligands by X-ray- and neutron-diffraction
Paper

Computational analysis of M–O covalency in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, U)

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

Graphical abstract: Computational analysis of M–O covalency in M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, U)
Paper

Isolation of reactive Ln(II) complexes with C5H4Me ligands (CpMe) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-CpMe)K(18-crown-6)][CpMe3LnII] (Ln = Tb, Ho)

We report that crystallographically-characterizable Ln(II) complexes of Tb and Ho can be isolated by reducing CpMe3Ln(THF) with KC8 in THF in the presence of 18-crown-6 (18-c-6).

Graphical abstract: Isolation of reactive Ln(ii) complexes with C5H4Me ligands (CpMe) using inverse sandwich countercations: synthesis and structure of [(18-crown-6)K(μ-CpMe)K(18-crown-6)][CpMe3LnII] (Ln = Tb, Ho)
Paper

Selective signalling of glyphosate in water using europium luminescence

Selective sensing of glyphosate in the micromolar regime in water.

Graphical abstract: Selective signalling of glyphosate in water using europium luminescence
34 items

About this collection

This special collection of Dalton Transactions is to mark the 65th birthday of mentor, friend and colleague, Professor Geoff Cloke. The collection highlights emerging trends in organometallic and coordination chemistry, reflecting the many diverse areas of where Geoff’s work has impacted the field, including catalysis and small-molecule activation chemistry involving transition metal and f-block elements, chemical bonding, mechanism, spectroscopy and magnetism.

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