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Themed collection Earth Abundant Element Compounds in Homogeneous Catalysis

42 items
Editorial

Earth abundant element compounds in homogeneous catalysis

Welcome to this themed issue of Dalton Transactions in the area of earth abundant element (EAE) compounds in homogeneous catalysis.

Graphical abstract: Earth abundant element compounds in homogeneous catalysis
Open Access Perspective

Aza-nickelacycle key intermediate in nickel(0)-catalyzed transformation reactions

Oxidative cyclization of alkynes and imines with nickel(0) is a key step in multicomponent coupling and cycloaddition reactions to give nitrogen-containing organic compounds.

Graphical abstract: Aza-nickelacycle key intermediate in nickel(0)-catalyzed transformation reactions
Open Access Perspective

Recent developments in alkene hydro-functionalisation promoted by homogeneous catalysts based on earth abundant elements: formation of C–N, C–O and C–P bond

This perspective provides an overview of the recent advancements in earth abundant element-based catalysts for alkene hydrofunctionalisation.

Graphical abstract: Recent developments in alkene hydro-functionalisation promoted by homogeneous catalysts based on earth abundant elements: formation of C–N, C–O and C–P bond
Communication

Ligand free copper(I)-catalyzed synthesis of diaryl ether with Cs2CO3via a free radical path

Complexes [Cu(I)(2,4-dimethylphenoxy)2] (A) and [Cu(II)(2,4-dimethylphenoxy)2(p-tolyl)] (B) were observed by in situ ESI-MS analysis of the ligand free copper(I)-catalyzed C–O coupling reaction using Cs2CO3 under the catalytic reaction conditions.

Graphical abstract: Ligand free copper(i)-catalyzed synthesis of diaryl ether with Cs2CO3via a free radical path
Communication

Catalytic aerobic oxidation of phenols to ortho-quinones with air-stable copper precatalysts

Air-stable Cu(II) species are competent precatalysts in the aerobic oxygenation of phenols into ortho-quinones.

Graphical abstract: Catalytic aerobic oxidation of phenols to ortho-quinones with air-stable copper precatalysts
Communication

Alkali metal-mediated dehydrocoupling of Me2NH·BH3

Bis(trimethylsilyl)amide derivatives of the group 1 elements (Li, Na, K) are competent pre-catalysts for the dehydrocoupling of Me2NH·BH3via the formation of intermediates containing [H3BNMe2BH2Me2N] anions.

Graphical abstract: Alkali metal-mediated dehydrocoupling of Me2NH·BH3
Communication

Cobalt-catalyzed ammonia borane dehydrocoupling and transfer hydrogenation under aerobic conditions

Simple cobalt compounds engage in ammonia borane dehydrocoupling and transfer hydrogenation.

Graphical abstract: Cobalt-catalyzed ammonia borane dehydrocoupling and transfer hydrogenation under aerobic conditions
Open Access Communication

Ring-opening polymerization of cyclohexene oxide using aluminum amine–phenolate complexes

Al(III) catalysts at concentrations as low as 0.001% ring-open cyclohexene oxide to yield high molecular weight polyether with narrow dispersity.

Graphical abstract: Ring-opening polymerization of cyclohexene oxide using aluminum amine–phenolate complexes
Communication

Regioselective synthesis of highly functionalized alkenylboronates by Cu-catalyzed borylation of propargylic silylalkynes

High regioselectivity was achieved in the Cu(I)-catalyzed borylation of internal propargylic alkynes with a silyl substituent to afford multifunctionalized alkenylboron compounds.

Graphical abstract: Regioselective synthesis of highly functionalized alkenylboronates by Cu-catalyzed borylation of propargylic silylalkynes
Communication

Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(II) complexes

Nickel(II) hydroxo compounds supported by an electron rich PCP pincer ligand are active catalysts for the selective hydration of a variety of nitriles at low catalyst loadings and mild conditions.

Graphical abstract: Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(ii) complexes
Paper

New findings and the current controversies for water oxidation by a copper(II)-azo complex: homogeneous or heterogeneous?

New findings for the water-oxidizing activity of [(L)CuII(NO3)], (L = (E)-3-(pyridin-2-yldiazenyl)naphthalen-2-ol (HL)) under both electro-water oxidation conditions and in the presence of cerium(IV) ammonium nitrate are reported.

Graphical abstract: New findings and the current controversies for water oxidation by a copper(ii)-azo complex: homogeneous or heterogeneous?
Paper

Titanium(IV) catalysts with ancillary imino-spiroketonato ligands: synthesis, structure and olefin polymerization

New titanium(IV) complexes having two bidentate β-iminoethyl-spiro[4,5]decan-6-onato ligands with various N-aryl substituents have been synthesized.

Graphical abstract: Titanium(iv) catalysts with ancillary imino-spiroketonato ligands: synthesis, structure and olefin polymerization
Paper

Titanium pyridonates for the homo- and copolymerization of rac-lactide and ε-caprolactone

A series of titanium pyridonate complexes have been synthesized under very mild reaction conditions from a common precursor, Ti(NMe2)4. These complexes have been explored as initiators for the ring-opening polymerization of rac-lactide and ε-caprolactone and have proven to be competitive with leading titanium initiators.

Graphical abstract: Titanium pyridonates for the homo- and copolymerization of rac-lactide and ε-caprolactone
Paper

Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene.

Graphical abstract: Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations
From the themed collection: In memory of Professor Kenneth Wade
Paper

Olefin polymerisation catalysts: when perfection is not enough

Despite decades of thorough mechanistic investigations, it is still hard to predict the activity of a novel olefin polymerisation catalyst, even when the precursor is a well-defined molecular entity. Kinetic studies using quenched-flow methods can help to understand why.

Graphical abstract: Olefin polymerisation catalysts: when perfection is not enough
Paper

Ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate catalyzed by magnesium and zinc complexes derived from binaphthyl-based iminophenolate ligands

Magnesium and zinc complexes derived from binaphthyl-based iminophenolate ligands efficiently initiated the ring-opening polymerization of rac-lactide and α-MeTMC, with the highest heteroselectivity (Pr = 0.84) or regioselectivity (Xreg = 0.98) obtained for the zinc complex.

Graphical abstract: Ring-opening polymerization of rac-lactide and α-methyltrimethylene carbonate catalyzed by magnesium and zinc complexes derived from binaphthyl-based iminophenolate ligands
Paper

Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane

Fe/Mn complexes of ethylene cross-bridged homocyclen catalyze oxygen atom transfer and hydrogen abstraction.

Graphical abstract: Synthesis, structural studies, kinetic stability, and oxidation catalysis of the late first row transition metal complexes of 4,10-dimethyl-1,4,7,10-tetraazabicyclo[6.5.2]pentadecane
Paper

Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship

High activity for the catalytic oxidation of 3,5-di-tert-butylcatechol was achieved with complexes of ligands that stabilize the biomimetic CuII μ-thiolate complex, hinting at a similarity with the required Cu-oxo intermediates.

Graphical abstract: Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship
Open Access Paper

P,O-Phosphinophenolate zinc(II) species: synthesis, structure and use in the ring-opening polymerization (ROP) of lactide, ε-caprolactone and trimethylene carbonate

Structurally diverse phosphinophenolate Zn(II) heteroleptic and homoleptic compounds are reported, some of which efficiently mediate the controlled ROP of lactide, ε-caprolactone and trimethylene carbonate under living and immortal conditions.

Graphical abstract: P,O-Phosphinophenolate zinc(ii) species: synthesis, structure and use in the ring-opening polymerization (ROP) of lactide, ε-caprolactone and trimethylene carbonate
Paper

Aluminium-catalysed intramolecular hydroamination of aminoalkenes: computational perusal of alternative pathways for aminoalkene activation

Rival mechanistic pathways for C[double bond, length as m-dash]C bond activation in aluminium-catalysed hydroamination: computational mechanistic analysis reveals that a catalytically relevant [(pda)Al(NHR)] compound promotes hydroamination through a stepwise σ-bond insertive mechanism with turnover-limiting aminolysis.

Graphical abstract: Aluminium-catalysed intramolecular hydroamination of aminoalkenes: computational perusal of alternative pathways for aminoalkene activation
Paper

Titanocene(III) complexes with 2-phosphinoaryloxide ligands for the catalytic dehydrogenation of dimethylamine borane

A study of the dehydrogenation of dimethylamine borane using different titanocene(III) complexes with 2-phosphinoaryloxide ligands is presented.

Graphical abstract: Titanocene(iii) complexes with 2-phosphinoaryloxide ligands for the catalytic dehydrogenation of dimethylamine borane
Open Access Paper

Magnesium amino-bis(phenolato) complexes for the ring-opening polymerization of rac-lactide

Magnesium complexes capable of rac-lactide polymerization in both the melt and in solution at elevated temperatures were synthesized. End-group analysis by MALDI-TOF showed both linear and cyclic PLA.

Graphical abstract: Magnesium amino-bis(phenolato) complexes for the ring-opening polymerization of rac-lactide
Paper

Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II)

Covalent tethering of a P2N2 ligand to a planar, azide-terminated glassy carbon electrode surface was accomplished using a CuI-catalyzed “click” reaction, followed by metallation with NiII.

Graphical abstract: Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(ii)
Paper

Stoichiometric and catalytic Si–N bond formation using the p-block base Al(NMe2)3

The aluminium reagent Al(NMe2)3 acts as a stoichiometric or catalytic reagent in dehydrogenic Si–N bond formation using amines and silanes. The observed catalytic rate law suggests a mechanism involving the silane component in the deprotonation of the amine.

Graphical abstract: Stoichiometric and catalytic Si–N bond formation using the p-block base Al(NMe2)3
From the themed collection: In memory of Professor Kenneth Wade
Paper

Synthesis and Lewis acidity of fluorophosphonium cations

A series of fluorophosphonium salts, [R3PF][X] (R = alkyl or aryl; X = FB(C6F5)3, [B(C6F5)4]), have been prepared by reactions of phosphine/borane frustrated Lewis pairs (FLPs) with XeF2 or difluorophosphoranes with [Et3Si][B(C6F5)4].

Graphical abstract: Synthesis and Lewis acidity of fluorophosphonium cations
Open Access Paper

Comparing a series of 8-quinolinolato complexes of aluminium, titanium and zinc as initiators for the ring-opening polymerization of rac-lactide

The preparation, characterization and properties of a series of 8-hydroxy quinolinolate complexes of Ti(IV), Al(III) and Zn(II) are presented. The complexes are active initiators for rac-lactide polymerizations: their performances are compared.

Graphical abstract: Comparing a series of 8-quinolinolato complexes of aluminium, titanium and zinc as initiators for the ring-opening polymerization of rac-lactide
Paper

Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues

Nickel POCOP-pincer hydride complexes react with phenylacetylene to afford alkenyl complexes whereas the palladium analogues give alkynyl complexes.

Graphical abstract: Reactions of phenylacetylene with nickel POCOP-pincer hydride complexes resulting in different outcomes from their palladium analogues
Paper

Vanadyl calix[6]arene complexes: synthesis, structural studies and ethylene homo-(co-)polymerization capability

Use of various combinations of [VOCl3], LiOt-Bu and p-tert-butylcalix[6]areneH6 affords vanadyl complexes capable of ethylene homo-(co-)polymerization.

Graphical abstract: Vanadyl calix[6]arene complexes: synthesis, structural studies and ethylene homo-(co-)polymerization capability
Paper

Synthesis of cyclic polyesters: effects of alkoxy side chains in salicylaldiminato tin(II) complexes

A new salicylaldiminato tin(II) catalyst system having alkoxy side chains has been developed and shown to effectively polymerize L-lactide and ε-caprolactone giving cyclic PLA and cyclic PCL, respectively.

Graphical abstract: Synthesis of cyclic polyesters: effects of alkoxy side chains in salicylaldiminato tin(ii) complexes
Paper

Ethylene polymerization by the thermally unique 1-[2-(bis(4-fluoro phenyl)methyl)-4,6-dimethylphenylimino]-2-aryliminoacenaphthylnickel precursors

Finely tuned substituents within ligands control the catalytic performance of the corresponding complex precursors, tailoring resulting polyethylenes.

Graphical abstract: Ethylene polymerization by the thermally unique 1-[2-(bis(4-fluoro phenyl)methyl)-4,6-dimethylphenylimino]-2-aryliminoacenaphthylnickel precursors
Paper

Iron catalysed Negishi cross-coupling using simple ethyl-monophosphines

Reported is a rare example of the use of monophosphines in iron catalysed Negishi cross-coupling. Substrate scope in terms of alkyl bromide and diaryl zinc reagent is explored.

Graphical abstract: Iron catalysed Negishi cross-coupling using simple ethyl-monophosphines
Paper

Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(III) corrole 1-Fe

The amphipolar iron(III) corrole 1-Fe is one of the most efficient catalysts for the decomposition of peroxynitrite, the toxin involved in numerous diseases.

Graphical abstract: Reaction mechanism for the highly efficient catalytic decomposition of peroxynitrite by the amphipolar iron(iii) corrole 1-Fe
Paper

Homochiral coordination cages assembled from dinuclear paddlewheel nodes and enantiopure ditopic ligands: syntheses, structures and catalysis

A series of homochiral (Cu2)2L4 lantern cages have been synthesized, which can promote cyclopropanation with up to 99 : 1 diastereoselectivity.

Graphical abstract: Homochiral coordination cages assembled from dinuclear paddlewheel nodes and enantiopure ditopic ligands: syntheses, structures and catalysis
Paper

Tetraphenolate niobium and tantalum complexes for the ring opening polymerization of ε-caprolactone

Reaction of the pro-ligands α,α,α′,α′-tetra(3,5-di-tert-butyl-2-hydroxyphenyl-p-(or -m-)xylene-para-(or -meta-)tetraphenol with [MCl5] (M = Nb, Ta) or [Nb(O)Cl3(NCMe)2] afforded complexes capable of the ROP of e-caprolactone at high temperature.

Graphical abstract: Tetraphenolate niobium and tantalum complexes for the ring opening polymerization of ε-caprolactone
Paper

(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis

The {CH(PPh2[double bond, length as m-dash]NSiMe3)(PPh2[double bond, length as m-dash]S)} ligand has been used for the synthesis of divalent and trivalent rare-earth borohydride complexes. These compounds enable the ring-opening polymerization (ROP) of ε-caprolactone (CL) and trimethylene carbonate (TMC).

Graphical abstract: (Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis
Paper

Ethylene polymerisation and ethylene/norbornene copolymerisation by using aryloxo-modified vanadium(V) complexes containing 2,6-difluoro-, dichloro-phenylimido complexes

V(N-2,6-X2C6H3)Cl2(O-2,6-R2C6H3) (X = Cl, F; R = Me, F) showed remarkable activity in ethylene polymerisation and the copolymerisation with norbornene in the presence of Et2AlCl.

Graphical abstract: Ethylene polymerisation and ethylene/norbornene copolymerisation by using aryloxo-modified vanadium(v) complexes containing 2,6-difluoro-, dichloro-phenylimido complexes
Open Access Paper

Intermolecular hydroaminoalkylation of alkenes and dienes using a titanium mono(formamidinate) catalyst

A titanium mono(formamidinate) complex catalyzes the hydroaminoalkylation of unactivated, sterically demanding, disubstituted alkenes and styrenes with secondary amines.

Graphical abstract: Intermolecular hydroaminoalkylation of alkenes and dienes using a titanium mono(formamidinate) catalyst
Paper

Metallacyclic yttrium alkyl and hydrido complexes: synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination

Yttrium complexes – efficient precatalysts for intermolecular olefin hydrophosphination and hydroamination.

Graphical abstract: Metallacyclic yttrium alkyl and hydrido complexes: synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination
Paper

Mono-, di- and tetra-zinc complexes derived from an amino-benzotriazole phenolate ligand containing a bulkier N-alkyl pendant arm: synthesis, structure and catalysis for ring-opening polymerization of cyclic esters

Tetranuclear alkoxide 3 with a saddle-shaped Zn4O4 conformation was an active initiator for living ROP of ε-caprolactone and β-butyrolactone.

Graphical abstract: Mono-, di- and tetra-zinc complexes derived from an amino-benzotriazole phenolate ligand containing a bulkier N-alkyl pendant arm: synthesis, structure and catalysis for ring-opening polymerization of cyclic esters
Paper

Catalytic behaviour in the ring-opening polymerisation of organoaluminiums supported by bulky heteroscorpionate ligands

A series of alkyl organoaluminium complexes based on bulky heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters.

Graphical abstract: Catalytic behaviour in the ring-opening polymerisation of organoaluminiums supported by bulky heteroscorpionate ligands
Paper

Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand

A series of “diamond-core” bridged dinuclear first-row transition metal complexes with the dinucleating ligand DPFN are prepared and characterized.

Graphical abstract: Dinuclear first-row transition metal complexes with a naphthyridine-based dinucleating ligand
Paper

Exploring the decomposition pathways of iron asymmetric transfer hydrogenation catalysts

An iron ATH catalyst is slowly transformed into an inactive, achiral iron complex under catalytic conditions.

Graphical abstract: Exploring the decomposition pathways of iron asymmetric transfer hydrogenation catalysts
42 items

About this collection

Guest Edited by Professors Philip Mountford (University of Oxford), Laurel L. Schafer (University of British Columbia) and Warren E. Piers (University of Calgary), this themed issue showcases the latest research in the development of highly active and selective homogeneous catalysts utilizing earth abundant elements from across the periodic table.

Spotlight

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