Themed collection 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.

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.

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.

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

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.

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

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.

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

A di(o-tolyl)borylgold complex added to CO/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.

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.

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

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

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.

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)₂(η⁴-P₄))Ag}₈]⁸⁺ of 2.49 nm in size based on an organometallic complex with a cyclo-P₄ end-deck.

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 ( = silicon).

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

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

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.

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

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.

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.

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.

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.

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

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

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.

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

Reactions of a magnesium diboranate as a source of [Bpin]⁻ anions are initiated by ‘outer sphere’ attack of CN bonded substrates.

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.

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.