Themed collection Inorganic chemistry of the p-block elements

This special web collection of Dalton Transactions focuses on the inorganic chemistry of the p-block elements, as a tribute to the 150th anniversary of the development of the periodic table.

This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen molecules, especially nitrogen-rich systems, with a focus of new structures, bonding insights and applications.

Recent outstanding advances in the C–Se bond formation through transition metalcatalysed direct selanylation, providing new insights into their mechanistic aspects, were provided in this perspective.

This perspective presents a concise overview of the developments in telluraporphyrinoid chemistry since its inception.

We highlight recent advances in organopnictogen chemistry contrasting the properties of lighter and heavier pnictogens.

Mechanistic insights into different modes of activation of hypercoordinate iodine(III) compounds.

Ring strain wins over entropy in the formation of inter- vs. intramolecularly 3c2e Si–H–Si bridged oligosilanylsilyl cations.

A stable 1,4-disilabenzene was generated from the reaction of a stable disilyne with 3-hexyne.

The suitability of phosphaphenalene derivatives for light-emitting diodes and electrofluorochromic devices is herein demonstrated.

The reactions of 9-phenyl-9-borafluorene with trimethylsilyldiazomethane in a 1 : 1 and 1 : 2 stoichiometry furnished the corresponding BC₅ and BC₆ heterocycles via the formal insertion of one and two carbene units.

A hydrogen-bridging tetraborane(6) was synthesized from boryllithium, a boron nucleophile, in three steps.

Persulfurated asterisks functionalized with six carboxylic groups form a strongly green phosphorescent coordination polymer upon addition of Pb²⁺ ions in aqueous solution. The self-assembly process is selective and reversible, enabling Pb²⁺ sensing with a detection limit of 6.0 × 10⁻⁷ M.

The redox reactivity of a stable anionic dithiolene radical has been explored, giving the corresponding dithiolate and neutral dithiolene dimers.

The reactions of germylone 1 with one equivalent of [M(COD)Cl]₂ (M = Ir, Rh) afforded the germylone-bridged bimetallic complexes 2 and 3, which have been spectroscopically and structurally characterized.

The synthesis of the highly soluble salts [Cu(CH₃CN)_3.5][FAl{OC(C₆F₁₀)(C₆F₅)}₃] and [Cu(CH₃CN)₄][Al{OC(CF₃)₃}₄] is presented. These compounds react with polyphosphorus ligand complexes to form pristine phosphorus-rich Cu(I) dimers.

Reactions between (Me₂PCH₂AlMe₂)₂ and late transition metal complexes led to five distinct outcomes, ranging from Me₂PCH₂AlMe₂ coordination to in situ generation of a tris(phosphino)aluminate ligand.

Highly symmetric enneanuclear copper(II) phosphates comprising of a hexanuclear and a trinuclear motif are described.

A series of tin(IV) halide complexes with mono- and bidentate pnictine ligands and the influence of various halide abstractors on these is discussed, together with DFT calculations to probe the HOMO/LUMO energies in the resulting species.

A comparison of structure and bonding in reduced formazanate B/Al complexes and their ligand-benzylated products is described. The kinetics of homolytic N–C(benzyl) bond cleavage in the latter compounds is studied.

Dinitrogen, one of the most nonpolar ligands in coordination chemistry, is known to be affected by electrostatic interactions in both heterogeneous and homogeneous reactions, but the significance of these effects is still poorly understood.

Boron-rich carboxylic acid derivatives were synthesised as coupling partners for tumour-selective biomolecules with applications as selective BNCT agents.

The reactivity of the germylene Ge(^tBu₂bzam)Mes with [Ir₂(μ-Cl)₂(η⁴-cod)₂] and [Ir₂Cl₂(μ-Cl)₂(η⁵-Cp*)₂] differs considerably from that previously communicated for the isostructural silylene Si(^tBu₂bzam)Mes.

The synthesis of a series of tetraorganoditelluronic acids, [RR′Te(μ-O)(OH)₂]₂ has been reported.

The conjoint effort of the –CH₂–CH₂– linker backbone and coordinating sites in the tetradentate ligand stabilizes a variety of stannylenes.

First synthesis of Pd₃P_0.95 QDs via solvent-controlled SSP and their three applications as catalysts (1–2 mol% of Pd) for substrates >10 are reported.

A tetrasilabicyclo[1.1.0]but-1(3)-ene was synthesized as orange crystals and its reactions were investigated.

Aluminium borohydrides of the type (Nacnac)Al(R){H₂(9-BBN)} are characterized by borane dissociation in solution under ambient conditions. This behaviour is critical to the ability of such complexes to reduce CO₂.

The rich reactivity of tetrylene dihalides towards a metallic FLP: phosphine exchange reactions and formation of homo and heterobimetallic compounds.

The reactions of an N/Al FLP-based aluminum hydride with a terminal alkyne yielded the deprotonated alumination compound, while that with an internal alkyne yielded a hydroalumination product.

2,6-Bisimino-4-alkyl-1,4-dihydropyridines provide access to dihydropyridinate(−1) aluminium(III) dialkyls, their double cycloaddition dimerization products and metal free ditopic ligands after controlled methanolysis.

Investigations of ene reactions between (F₃C)₂BNMe₂ and substituted propenes reveal additive substitutional effects on barriers and reaction energies.

We report a series of room temperature phosphorescent compounds 1–6 composed of triarylborane (TAB) and cyclometallated iridium complexes.

A new iodine catalyst was supported in two different MOFs and the catalytic activity for the oxidation of hydroquinones and catechols was evaluated.

New aluminates as active catalysts for vinyl polymerization are described, as well as a strategy to crosslinked polymers from GMA in a controlled fashion.

Studies on [Ln₄(LH₂)₂(O₃P^tBu)₂(μ₂-η¹η¹tfa)₂]·2Cl (Ln = Dy^III, Tb^III and Gd^III) reveal a SMM behaviour for the Dy^III analogue and a SMT behaviour for the Tb^III analogue.

Alumoxane and aluminum dihydrides activate CO₂ producing unusual inorganic cores while reactions with CS₂ produce cyclic alumoxane and aluminum sulfides.

Silanes and phosphines are photocatalytically oxidized with a self-sensitized tellurorhodamine under aerobic conditions.

An NHC-stabilized three-coordinate hydrosilylene dehydrogenates ammonia borane and forms more stable complexes with BH₃, BPh₃, BBr₃ and BPhBr₂ but less stable ones with BF₃, and BCl₃ for which ligand scrambling occurs.

Three new manganese carbonyl compounds with heavy atom donors were synthesized and their potential use as photoCORMS was evaluated.

Reactions of aluminate anions [EtAl(6-R-2-py)₃]⁻(6-R-2-py = 6-R-2-pyridyl, R = Me or Br) with aldehydes (RCHO) or carboxylic acids (RCO₂H) reveal how these species can be used to sense chirality and show a new aspect of isomerism in this area.

Catalytic hydroboration of alkenes is reported using the redox active phenalenyl ligand assisted nickel complex Ni(PLY)₂(THF)₂ in the presence of pinacolborane under ambient conditions.

The synthesis of mixed hexasubstituted benzenes bearing alternate heteroatoms (O, S and Se) is described. The potential of these species as “turn-off” chemical sensors for Cu²⁺, which is a biologically and environmentally crucial metal ion, is also successfully demonstrated.

The synthesis and structure of well-defined arylelement chlorides RSnCl₄, RSnCl₃·THF, RSbCl₂, RSbCl₂·THF and RBiCl₂ is reported (R = 6-diphenylphosphinoxy-acenapth-5-yl).

The ability of different ligands to attract a pendant amine is studied in a series of iron complexes.

Tetramers of iso-tellurazole N-oxides form stable macrocyclic complexes with Pt(II) and Rh(III) in solution.

A new family of mononuclear Ln^III complexes were synthesized by utilizing a tridentate Schiff base ligand. SIM behaviour is seen in the Dy^III analogue (diluted) with U_eff = 68(2) K under a 1000 Oe applied dc field.

1-(Trimethylsilyl)propyne 2a reacts with halogenoboranes XB(C₆F₅)₂ (X: Cl, Br) in a 2 : 1 molar ratio under mild conditions by consecutive 1,1-carboboration reactions to give the highly substituted boryldienes 4.

The synthesis and activity of the first polymeric frustrated Lewis pairs for the borylation of heteroarenes is reported.

The synthesis and reactivity of salen supported OCP adducts of aluminium and gallium is reported.

Helical aluminium complexes have been prepared and used as catalysts for cyclic carbonate synthesis.

An unusual trimetallic octaselenide complex, [(Cp*Ta)₃(μ-Se)₄{μ-Se₂(Se₂)}], has been synthesized and structurally characterized.

Ir–NSi^tBu based catalysts allow the control of the selective reduction of formamides with HSiMe₂Ph to afford O-silylated hemiaminals or methylamines.

Metal complexes that form isolable, ligand-centered borenium ions (i.e. reactive three-coordinate boron cations) are rare, especially with highly-versatile diphosphorus ligands.

Novel primary phosphanes with bulky 2,6-bis(benzhydryl)phenyl substituents could be prepared and fully characterized.

Compounds [(R¹GeCl)₂E₂] were isolated upon reactions of R¹GeCl₃ (R¹ = CMe₂CH₂COMe) with (Me₃Si)₂E (E = S, Se, Te) as intermediates of the [(R¹Ge)₄E₆] cluster formation.

This paper describes the syntheses of two novel cyclodiphosphazane derivatives and their coordination chemistry with Cu^I, Ru^II, Rh^I, Pd^II and Au^I is also described.

A cobalt N-heterocyclic phosphido complex is shown to cleave element–hydrogen bonds via a metal–phosphorus ligand cooperative pathway.

This work provides a rare example of high coordination of a nitro-selenidovanadium(III) complex with photocurrent response properties.

Two metal–organic frameworks (MOFs) made of indium and 1,3,5-tris(4-carboxyphenyl)benzene and having a layered structure have been synthesized, showing catalytic activity in the one-pot Ugi reaction.

An efficient strategy for enhancing CO₂ capture performance based on 2-hydroxyl pyridium anion-functionalized ILs was reported via the reduction of cation–anion interactions in ILs.

Key structural and optoelectronic features of 2,3,6,7-tetraarylated diboraanthracenes were compared with those of corresponding singly and doubly ring-closed diboratetracenes and -pentacenes.

Depending on the Sn(II) compound used, reactions with two equivalents of azide led to the formation of tetrazastanols [R₂N₄SnR′₂] or cyclo-distannadiazanes [R₂Sn(μ-NR′)]₂.

3,5-Bicyclic aryl piperidines are derivatized to generate chiral B/N FLPs. The Lewis acidities were assessed by experimental and computational methods. The activity in HD scrambling and hydrogenation was also assessed. These data demonstrate that a threshold of combined Lewis acidity and basicity is essential to activate H₂.

Ionized methylalumoxane exchanges alkyl groups rapidly with trialkylaluminums in solution, generating statistical mixtures of modified methylalumoxane anions.