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Themed collection Frontiers in Molecular Main Group Chemistry

40 items
Editorial

Frontiers in Molecular Main Group Chemistry: a web themed issue

The diversity of Main Group inorganic and organometallic chemistry is encapsulated in this web themed issue.

Graphical abstract: Frontiers in Molecular Main Group Chemistry: a web themed issue
From the themed collection: Frontiers in Molecular Main Group Chemistry
Feature Article

Molecular early main group metal hydrides: synthetic challenge, structures and applications

Ligand-stabilized early main group metal hydride clusters.

Graphical abstract: Molecular early main group metal hydrides: synthetic challenge, structures and applications
From the themed collection: Aromaticity
Feature Article

Polyimido sulfur anions and ylides

Polyimido sulfur anions and ylides provide a rich scope of different coordination modes to various metals due to their different charges and donor sites.

Graphical abstract: Polyimido sulfur anions and ylides
From the themed collection: Frontiers in Molecular Main Group Chemistry
Feature Article

Main group pyridyl-based ligands; strategies to mixed metal complexes

This review highlights new classes of main group tris-2-pyridyl ligands of the type [Y(2-py)3]n containing metallic or semi-metallic bridgehead atoms (Y) and explores the way in which they can be used to form heterometallic complexes in a targeted way.

Graphical abstract: Main group pyridyl-based ligands; strategies to mixed metal complexes
From the themed collection: Frontiers in Molecular Main Group Chemistry
Feature Article

Activation of phosphorus by group 14 elements in low oxidation states

In this feature article we describe the activation of phosphorus using compounds with low valent group 14 elements.

Graphical abstract: Activation of phosphorus by group 14 elements in low oxidation states
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Making practical use of the pseudo-element concept: an efficient way to ternary intermetalloid clusters by an isoelectronic Pb–Bi combination

Soluble [K([2.2.2]crypt)]+ salts of pseudo-homoatomic Pb–Bi Zintl anions readily react with ZnPh2 or Ni(cod)2 to yield ternary intermetalloid Ni–Pb–Bi or Zn–Pb–Bi clusters in a highly efficient way.

Graphical abstract: Making practical use of the pseudo-element concept: an efficient way to ternary intermetalloid clusters by an isoelectronic Pb−–Bi combination
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Alkynide and acetonitrile activation by strained AlPC2 heterocycles

Four-membered AlPC2 heterocycles react as “masked Frustrated Lewis Pairs” by ring opening and activation of small molecules such as acetonitrile.

Graphical abstract: Alkynide and acetonitrile activation by strained AlPC2 heterocycles
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Endocyclic P–P bond cleavage in carbaborane-substituted 1,2-diphosphetane: a new route to secondary phosphinocarbaboranes

Carbaborane-substituted 1,2-diphosphetane reacts with lithium and hydrogen chloride to give a secondary bis(phosphino)carbaborane, which is a suitable precursor for carbaborane-substituted 1-aza-3,6-diphosphepanes.

Graphical abstract: Endocyclic P–P bond cleavage in carbaborane-substituted 1,2-diphosphetane: a new route to secondary phosphinocarbaboranes
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

[(η2-(Si/Ge)4)Zn(η2-(Si/Ge)4)]6− – novel Zintl clusters with mixed Si/Ge tetrahedra bridged by a Zn atom

Dimeric tetrahedral Zintl clusters [(η2-E4)Zn(η2-E4)]6− (E = Si/Ge) were obtained from ammonia solutions of the ternary Zintl phase K12Si17−xGex (x = 5).

Graphical abstract: [(η2-(Si/Ge)4)Zn(η2-(Si/Ge)4)]6− – novel Zintl clusters with mixed Si/Ge tetrahedra bridged by a Zn atom
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Synthesis of a stable 1,2-bis(ferrocenyl)diphosphene

A novel d–π electron system: 1,2-bis(ferrocenyl)diphosphene.

Graphical abstract: Synthesis of a stable 1,2-bis(ferrocenyl)diphosphene
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

A 32 vertex polyhedron via supramolecular assembly of silanedithiolate silanolate units

A silanedithiolate silanolate assembles spontaneously forming an inorganic rugby ball shaped 32 vertex polyhedral cluster stabilized by organic substituents and LiCl.

Graphical abstract: A 32 vertex polyhedron via supramolecular assembly of silanedithiolate silanolate units
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Donor–acceptor stabilized silaformyl chloride

Silicon analogue of the formyl chloride, silaformyl chloride IPr·SiH(Cl)[double bond, length as m-dash]O·B(C6F5)3 (IPr = 1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene) was stabilized by Lewis donor–acceptor ligands.

Graphical abstract: Donor–acceptor stabilized silaformyl chloride
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Dimethylamine borane dehydrogenation chemistry: syntheses, X-ray and neutron diffraction studies of 18-electron aminoborane and 14-electron aminoboryl complexes

The reactions of Me2NH·BH3 with cationic Rh(III) and Ir(III) complexes have been shown to generate an 18-electron aminoborane adduct and a 14-electron aminoboryl complex.

Graphical abstract: Dimethylamine borane dehydrogenation chemistry: syntheses, X-ray and neutron diffraction studies of 18-electron aminoborane and 14-electron aminoboryl complexes
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Me3P complexes of p-block Lewis acids SnCl4, SnCl3+ and SnCl22+

Prototypical Me3P complexes of SnCl3+ and SnCl22+, and of SnCl4 illustrate fundamental bonding environments for tin.

Graphical abstract: Me3P complexes of p-block Lewis acids SnCl4, SnCl3+ and SnCl22+
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

The Cp*Si+ cation as a stoichiometric source of silicon

Cp*Si+ acts as a stoichiometric source of silicon in the reaction with a disilenide.

Graphical abstract: The Cp*Si+ cation as a stoichiometric source of silicon
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Synthesis and reactivity of cationic ruthenium germylene complexes [Cp*(PiPr3)RuH2([double bond, length as m-dash]GeRR′)]+

Two synthetic routes to cationic ruthenium germylene complexes are described, and a hydrogen-substituted germylene complex was found to undergo rapid additions of the Ge–H bond to unsaturated substrates.

Graphical abstract: Synthesis and reactivity of cationic ruthenium germylene complexes [Cp*(PiPr3)RuH2( [[double bond, length as m-dash]] GeRR′)]+
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Water compatibility and organic transformations of organo-Zintl deltahedral clusters

Amazingly, the di-substituted deltahedral Zintl ions [Ge9R2]2− are stable in the presence of water, and this has been exploited in a Schiff-base reaction producing water as a byproduct.

Graphical abstract: Water compatibility and organic transformations of organo-Zintl deltahedral clusters
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Tricationic analogues of boroxines and polyborate anions

Addition of E2O (E = Me3Si or H) to [(pyridyl)BX2][AlX4] (X = Cl or Br) and subsequent heating produced the unprecedented trications [(2,6-lutidine)4B5O6]3+ and [(pyridine)4B3O3]3+.

Graphical abstract: Tricationic analogues of boroxines and polyborate anions
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

P–P Menschutkin preparation of prototypical phosphinophosphonium salts

Prototypical phosphinophosphonium cations are synthesized from phosphines and halophosphines, illustrating the versatility of the Menschutkin reaction for E–E bond formation.

Graphical abstract: P–P Menschutkin preparation of prototypical phosphinophosphonium salts
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Stepwise activation of “non-innocent” Cp* substituents – a Cp* based cascade reaction

Reactions of Cp* substituted pentelidene complexes with the primary phosphine Cp*PH2 yield novel polycyclic phosphorus/arsenic and carbon containing cage compounds via cascade-like reactions.

Graphical abstract: Stepwise activation of “non-innocent” Cp* substituents – a Cp* based cascade reaction
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

One-step conversion of methoxysilanes to aminosilanes: a convenient synthetic strategy to N,O-functionalised organosilanes

A straightforward substitution of silicon-bonded methoxy groups by a lithium amide is presented, providing mixed N,O-precursors for chemoselective transformations.

Graphical abstract: One-step conversion of methoxysilanes to aminosilanes: a convenient synthetic strategy to N,O-functionalised organosilanes
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Intermediates in the Rh-catalysed dehydrocoupling of phosphine–borane

Active species, product distributions and a suggested catalytic cycle are reported for the dehydrocoupling of the phosphine–borane H3B·PtBu2H to give HPtBu2BH2PtBu2BH3 using the [Rh(COD)2][BArF4] pre-catalyst.

Graphical abstract: Intermediates in the Rh-catalysed dehydrocoupling of phosphine–borane
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Calciate-mediated intermolecular hydroamination of diphenylbutadiyne with secondary anilines

Calcium-mediated hydroamination of diphenylbutadiyne succeeds once even with rather weak nucleophiles such as diphenylamine employing heterobimetallic K2Ca(NR2)4.

Graphical abstract: Calciate-mediated intermolecular hydroamination of diphenylbutadiyne with secondary anilines
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Cyclic and polycyclic tellurium–tin and tellurium–lead compounds – synthesis, structures and thermal decomposition

The uncommon tin–tellurium cluster [{(Me3Si)3SiTe}4Te2Sn4] as well as other Sn–Te and Pb–Te compounds are described.

Graphical abstract: Cyclic and polycyclic tellurium–tin and tellurium–lead compounds – synthesis, structures and thermal decomposition
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

The elusive tripodal tris(2-pyridyl)borate ligand: a strongly coordinating tetraarylborate

Tris(2-pyridyl)borates are introduced as a new robust and tunable ligand family that combines the desirable complexation behavior of “scorpionate” ligands with the high stability of weakly coordinating arylborate anions.

Graphical abstract: The elusive tripodal tris(2-pyridyl)borate ligand: a strongly coordinating tetraarylborate
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Alkynyl-functionalised and linked bicyclo[1.1.1]pentanes of group 14

The preparation and structures of the first alkynyl-functionalised and catenated Sn2Si3 bicyclo[1.1.1]pentanes are reported, together with NMR spectroscopic and computational studies of their properties.

Graphical abstract: Alkynyl-functionalised and linked bicyclo[1.1.1]pentanes of group 14
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Transmetallation reactions of a lithium disilenide

The first magnesium, copper and zinc disilenides were prepared via transmetallation reactions of a lithium disilenide and structurally characterised. The copper and zinc derivatives show red-shifted UV/vis absorptions due to admixture of metal d-orbitals to the highest occupied molecular orbital.

Graphical abstract: Transmetallation reactions of a lithium disilenide
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Rhenium complexes bearing phospholepyridine chelates: simple molecules with large chiroptical properties

The synthesis and chiroptical properties of chiral rhenium complexes bearing mono- or di-topic phosphole ligands are described.

Graphical abstract: Rhenium complexes bearing phosphole–pyridine chelates: simple molecules with large chiroptical properties
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Planar P6E6 (E = Se, S) macrocycles incorporating P2N2 scaffolds

The 15-membered rings [(tBuN)P(μ-NtBu)2P(NtBu)(μ-E–E)]3 (E = Se, S) are comprised of planar P6E6 motifs stabilised by perpendicular P2N2 rings.

Graphical abstract: Planar P6E6 (E = Se, S) macrocycles incorporating P2N2 scaffolds
Communication

Synthesis of 1,2,3-tripnictolide anions by reaction of group 15 Zintl ions with acetylene. Isolation of [E3C2H2] (E = P, As) and preliminary reactivity studies

We report a convenient synthesis of 1,2,3-tripnictolide anions and their subsequent reactivity towards a transition metal organometallic reagent.

Graphical abstract: Synthesis of 1,2,3-tripnictolide anions by reaction of group 15 Zintl ions with acetylene. Isolation of [E3C2H2]− (E = P, As) and preliminary reactivity studies
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Reactivity of terminal phosphinidene versus Li–Cl phosphinidenoid complexes in cycloaddition chemistry

The first comparative study on reactions of the title reactive intermediates with a conjugated π-system reveals a significantly increased selectivity of the Li–Cl phosphinidenoid complex; DFT calculations provide a first explanation based on a lithium cation template in a stepwise formal [4+1] cycloaddition reaction.

Graphical abstract: Reactivity of terminal phosphinidene versus Li–Cl phosphinidenoid complexes in cycloaddition chemistry
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

An inorganic propellane with central B–B bond

1 reacts with 2-mercaptoimidazole (HmtiPr) to afford the [4.3.3]propellane 5. The EI mass spectra of 1 and 5 are dominated by fragments corresponding to [anthracene]+˙ and [B2R2]+˙ (R = NMe2, mtiPr).

Graphical abstract: An inorganic propellane with central B–B bond
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Alkali-metal mediated reactivity of a diaminobromoborane: mono- and bis-borylation of naphthalene versus boryl lithium or hydroborane formation

We report varied reduction reactions of a sterically demanding diaminobromoborane which are mediated by the nature of the alkali metal reductant.

Graphical abstract: Alkali-metal mediated reactivity of a diaminobromoborane: mono- and bis-borylation of naphthalene versus boryl lithium or hydroborane formation
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Diborane(4)–metal bonding: between hydrogen bridges and frustrated oxidative addition

Frozen early stages of oxidative additions and B–H–metal interactions are two schemes in complexes of a specific doubly-base-stabilised diborane(4).

Graphical abstract: Diborane(4)–metal bonding: between hydrogen bridges and frustrated oxidative addition
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

A début for base stabilized monoalkylsilylenes

Facile syntheses of monoalkylsilylenes LSitBu (2) and LSi[C(SiMe3)3] (3) by metathesis reaction of LitBu and KC(SiMe3)3 with LSiCl (1) (L = PhC(NtBu)2).

Graphical abstract: A début for base stabilized monoalkylsilylenes
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Magnesium-catalysed hydroboration of aldehydes and ketones

The heteroleptic magnesium alkyl complex [CH{C(Me)NAr}2MgnBu] (Ar = 2,6-iPr2C6H3) is reported as a highly efficient pre-catalyst for the hydroboration of aldehydes and ketones with pinacolborane.

Graphical abstract: Magnesium-catalysed hydroboration of aldehydes and ketones
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition

Phosphine-boronates R2P(o-C6H4)B(OR′)2 have been evaluated as bifunctional organocatalysts for Michael addition reactions. Isolation of a key β-phosphonium enolate intermediate has substantiated the role of the Lewis acidic moiety.

Graphical abstract: Phosphine-boronates: efficient bifunctional organocatalysts for Michael addition
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Contrasting reductions of group 14 metal(II) chloride complexes: synthesis of a β-diketiminato tin(I) dimer

Reductions of group 14 metal(II) chloride complexes with a magnesium(I) dimer have led to significantly different outcomes, including the formation of the first β-diketiminato tin(I) dimer (see picture).

Graphical abstract: Contrasting reductions of group 14 metal(ii) chloride complexes: synthesis of a β-diketiminato tin(i) dimer
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

New lithium-zincate approaches for the selective functionalisation of pyrazine: direct dideprotozincation vs. nucleophilic alkylation

Two new ligand-dependent lithium-zincate methodologies (via two-fold deprotonation or C–H alkylation) are disclosed for the selective functionalisation of pyrazine.

Graphical abstract: New lithium-zincate approaches for the selective functionalisation of pyrazine: direct dideprotozincation vs. nucleophilic alkylation
From the themed collection: Frontiers in Molecular Main Group Chemistry
Communication

Efficient generation of stable adducts of Si(II) dihydride using a donor–acceptor approach

An efficient synthesis of the stable Si(II) dihydride complex IPr·SiH2·BH3 (IPr = [(HCNDipp)2C:]; Dipp = 2,6-iPr2C6H3) is reported.

Graphical abstract: Efficient generation of stable adducts of Si(ii) dihydride using a donor–acceptor approach
From the themed collection: Frontiers in Molecular Main Group Chemistry
40 items

About this collection

This web-based themed issue features a collection of Communications and Feature Articles from prominent scientists working on all aspects of molecular main group chemistry. The themed issue will cover a wide range of s-block and p-block chemistry, from new fundamental studies to novel applications of main group compounds in synthesis, catalysis and materials.

The guest editors for this issue are Manfred Scheer (University of Regensburg) and Richard Layfield (University of Manchester).

Articles in this web themed issue will be added below as soon as possible after they are published. Please return to this page frequently to see the collection grow.

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