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Themed collection Spotlighting main group elements in polynuclear complexes

30 items
Open Access Editorial

Spotlighting main group elements in polynuclear complexes

François Gabbaï, Cameron Jones and Connie Lu introduce the Chemical Science themed collection on the topic of main group elements in polynuclear complexes.

Graphical abstract: Spotlighting main group elements in polynuclear complexes
Open Access Perspective

Main group bimetallic partnerships for cooperative catalysis

Exporting cooperative effects in main group heterobimetallic reagents to catalytic regimes, this Perspective showcases key advances in their applications for hydroelementation, cyclisation, C–C bond formation and polymerization processes.

Graphical abstract: Main group bimetallic partnerships for cooperative catalysis
From the themed collection: Chemical Science Recent Perspective articles
Open Access Perspective

Catalysis using transition metal complexes featuring main group metal and metalloid compounds as supporting ligands

Recent development in catalytic application of transition metal complexes having an M–E bond (E = main group metal or metalloid element), which is stabilized by a multidentate ligand, is summarized.

Graphical abstract: Catalysis using transition metal complexes featuring main group metal and metalloid compounds as supporting ligands
From the themed collection: Chemical Science Recent Perspective articles
Open Access Minireview

Catalytic C–H to C–M (M = Al, Mg) bond transformations with heterometallic complexes

This highlight focuses on recent efforts to establish catalytic methods for C–H functionalisation with main group metals (M = Al, Mg).

Graphical abstract: Catalytic C–H to C–M (M = Al, Mg) bond transformations with heterometallic complexes
Open Access Minireview

Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis

This minireview highlights the recent advances in small molecule activation and catalytic applications of homonuclear dimetallenes, dimetallynes and interconnected bismetallylenes of heavier group 14 elements.

Graphical abstract: Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis
Open Access Minireview

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

The application of ylide substituents as strong donor ligands for the stabilization of reactive main group compounds with unusual properties and reactivities is discussed.

Graphical abstract: Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds
Open Access Edge Article

Ambiphilic boryl groups in a neutral Ni(II) complex: a new activation mode of H2

A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process.

Graphical abstract: Ambiphilic boryl groups in a neutral Ni(ii) complex: a new activation mode of H2
Open Access Edge Article

Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(II) complex [Pt(ItBuiPr′)(ItBuiPr)][BArF], 1, with tricoordinated boranes HBR2.

Graphical abstract: Reversible carbon–boron bond formation at platinum centers through σ-BH complexes
Open Access Edge Article

Nucleophilic reactivity of the gold atom in a diarylborylgold(I) complex toward polar multiple bonds

A di(o-tolyl)borylgold complex added to C[double bond, length as m-dash]O/N double bond to form Au–C and B–O/N bonds. DFT calculations revealed a two-step mechanism consisting of the coordination of O/N atom to B atom followed by nucleophilic migration of Au atom.

Graphical abstract: Nucleophilic reactivity of the gold atom in a diarylborylgold(i) complex toward polar multiple bonds
Open Access Edge Article

Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis

The synthesis, characterization and computational analysis of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. White phosphorus was used to install the central phosphorus atom.

Graphical abstract: Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis
Open Access Edge Article

A cyclopentadienyl functionalized silylene – a flexible ligand for Si- and C-coordination

A cyclopentadienyl functionalized silylene or its derivatives can be coordinated in all three forms: silylene (A), anion (B), and sila fulvene (C).

Graphical abstract: A cyclopentadienyl functionalized silylene – a flexible ligand for Si- and C-coordination
Open Access Edge Article

Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene

(PBP)Ir pincer complexes containing a boryl-iridium linkage reversibly bind ethylene as an ethylidene bridging B and Ir.

Graphical abstract: Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene
Open Access Edge Article

Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes

We report a series of high spin bimetallic transition metal–tin complexes. The unusual high spin configuration in a bimetallic complex is enabled by an energetic mismatch in the orbital energies, leading to lanthanide-like nonbonding interactions.

Graphical abstract: Orbital energy mismatch engenders high-spin ground states in heterobimetallic complexes
Open Access Edge Article

Use of a cyclo-P4 building block – a way to networks of host–guest assemblies

A one-pot self-assembly template-controlled reaction is reported to result in a 2D coordination network of first host-guest assemblies P3Se4@[{(Cp′′Ta(CO)24-P4))Ag}8]8+ of 2.49 nm in size based on an organometallic complex with a cyclo-P4 end-deck.

Graphical abstract: Use of a cyclo-P4 building block – a way to networks of host–guest assemblies
Open Access Edge Article

Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization

Unprecedented metallasiliconoids are accessible from a silylene-substituted Si6 siliconoid and Group 9 metal fragments. The isomerization of terminal alkenes to 2-alkenes is competitively catalyzed by these species (Image ID:d0sc02861d-u1.gif = silicon).

Graphical abstract: Exohedral functionalization vs. core expansion of siliconoids with Group 9 metals: catalytic activity in alkene isomerization
Open Access Edge Article

BNN-1,3-dipoles: isolation and intramolecular cycloaddition with unactivated arenes

The mono-base-coordinated 1,2-diboranylidenehydrazine derivatives exhibiting the BNN-1,3-dipolar reactivity toward unactivated arenes and CO2 are reported.

Graphical abstract: BNN-1,3-dipoles: isolation and intramolecular cycloaddition with unactivated arenes
Open Access Edge Article

Heteroleptic actinocenes: a thorium(IV)–cyclobutadienyl–cyclooctatetraenyl–di-potassium-cyclooctatetraenyl complex

We report the first thorium–cyclobutadienyl complex, a new type of heteroleptic actinocene, that exhibits ‘an alkene-like’ thorium–η2-cyclooctatetraenyl interaction.

Graphical abstract: Heteroleptic actinocenes: a thorium(iv)–cyclobutadienyl–cyclooctatetraenyl–di-potassium-cyclooctatetraenyl complex
Open Access Edge Article

A highly unsaturated six-vertex amido-substituted silicon cluster

Thermal treatment of the bicyclo[1.1.0]tetrasilatetraamide [Si4{N(SiMe3)Dipp}4] 1 resulted in the formation of a highly unsaturated six-vertex silicon cluster [Si6{N(SiMe3)Dipp}4] 2 with only four amine-substituents and two ligand-free silicon atoms.

Graphical abstract: A highly unsaturated six-vertex amido-substituted silicon cluster
Open Access Edge Article

Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet

A series of fulvalene-supported dimetallic dysprosium metallocene SMMs provides a roadmap to poly-cationic dysprosocenium single-molecule magnets.

Graphical abstract: Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet
Open Access Edge Article

Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates

A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl]+, is a precursor to efficient catalysts for the hydrosilation of alkenes with hydrosilanes under mild conditions and low catalyst loadings.

Graphical abstract: Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates
Open Access Edge Article

Trends in trigonal prismatic Ln-[1]ferrocenophane complexes and discovery of a Ho3+ single-molecule magnet

Lanthanide ferrocenophanes are an intriguing class of organometallic complexes that feature rare six-coordinate trigonal prismatic coordination environments of 4f elements with close intramolecular proximity to iron ions.

Graphical abstract: Trends in trigonal prismatic Ln-[1]ferrocenophane complexes and discovery of a Ho3+ single-molecule magnet
Open Access Edge Article

Sterically controlled reductive oligomerisations of CO by activated magnesium(I) compounds: deltate vs. ethenediolate formation

Subtle changes to the bulk of 1 : 1 adducts of DMAP with magnesium(I) complexes leads to steric control over the products arising from their reductive oligomerisations of carbon monoxide.

Graphical abstract: Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation
Open Access Edge Article

A germaaluminocene

Boron vs. aluminum: the synthesis of a borole complex of Ge(II) is reported. Changing just the element from boron to aluminum unexpectedly yields an unprecedented neutral germaaluminocene.

Graphical abstract: A germaaluminocene
Open Access Edge Article

Differential uranyl(V) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study

Uranyl Pacman takes them all: the bonding of s- and d-block cations to uranyl is compared by experiment, spectroscopy and theory.

Graphical abstract: Differential uranyl(v) oxo-group bonding between the uranium and metal cations from groups 1, 2, 4, and 12; a high energy resolution X-ray absorption, computational, and synthetic study
Open Access Edge Article

CO2 reduction with protons and electrons at a boron-based reaction center

A redox-active borane enables CO2 reduction at boron with protons and electrons.

Graphical abstract: CO2 reduction with protons and electrons at a boron-based reaction center
Open Access Edge Article

Mild synthesis of diboryldiborenes by diboration of B–B triple bonds

A set of diboryldiborenes are prepared by the mild, catalyst-free, room-temperature diboration of the B–B triple bonds of doubly base-stabilized diborynes.

Graphical abstract: Mild synthesis of diboryldiborenes by diboration of B–B triple bonds
Open Access Edge Article

Thermodynamic and kinetic studies of H2 and N2 binding to bimetallic nickel-group 13 complexes and neutron structure of a Ni(η2-H2) adduct

Binding energies for H2 and N2 at nickel become more exergonic for the larger group 13 sigma-accepting supports.

Graphical abstract: Thermodynamic and kinetic studies of H2 and N2 binding to bimetallic nickel-group 13 complexes and neutron structure of a Ni(η2-H2) adduct
Open Access Edge Article

Snapshots of magnesium-centred diborane heterolysis by an outer sphere SN2 process

Reactions of a magnesium diboranate as a source of [Bpin] anions are initiated by ‘outer sphere’ attack of C[double bond, length as m-dash]N bonded substrates.

Graphical abstract: Snapshots of magnesium-centred diborane heterolysis by an outer sphere SN2 process
Open Access Edge Article

Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides

Pendent borane Lewis acids provide an avenue for changing a ligand's field strength through acid/base interactions; this strategy was highlighted within a series of biologically-relevant high spin iron hydrides.

Graphical abstract: Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
Open Access Edge Article

Heterodinuclear zinc and magnesium catalysts for epoxide/CO2 ring opening copolymerizations

Eight heterodinuclear catalysts comprising Zn(II) and Mg(II) metal centres show high activity and selectivity for CO2/epoxide ring-opening copolymerization. Detailed kinetic analyses are reported and a chain-shuttling mechanistic hypothesis proposed.

Graphical abstract: Heterodinuclear zinc and magnesium catalysts for epoxide/CO2 ring opening copolymerizations
30 items

About this collection

Associate Editor François Gabbaï and Guest Editors Cameron Jones and Connie Lu introduce this themed collection on the topic of main group elements in polynuclear complexes. This collection is made up of a selection of previously published Edge content that has been carefully selected by François, Cameron and Connie, to showcase what they feel represent recent achievements towards the incorporation of main group elements in polynuclear motifs or in the coordination sphere of transition metals, while at the same time illustrating far-reaching applications in the areas of small molecule activation, catalysis and molecular magnetism.

This collection also features some specially curated review content on the topics of Group 14 dimetallenes and dimetallynes, phosphorus-ylides, main group metal and metalloid ligands, cooperative catalysis, and magnesium and aluminium reductants in C–H bond activation.

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