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Themed collection Silicon Chemistry: Discoveries and Advances

25 items
Editorial

Current advances in the chemistry of silicon: not exactly a carbon copy

Welcome to this themed issue of Dalton Transactions entitled: ‘Silicon Chemistry: Discoveries and Advances.’

Graphical abstract: Current advances in the chemistry of silicon: not exactly a carbon copy
Communication

Functionalized vinylsilanes via highly efficient and recyclable Pt-nanoparticle catalysed hydrosilylation of alkynes

A mild, selective and facile synthesis of vinylsilanes via a recyclable platinum nanoparticle catalysed hydrosilylation of alkynes is reported.

Graphical abstract: Functionalized vinylsilanes via highly efficient and recyclable Pt-nanoparticle catalysed hydrosilylation of alkynes
Communication

Synthesis and structures of lithium alkoxytris(dimethylphenylsilyl)borates

The X-ray crystallography showed that the structures of the silyl-substituted borates are affected by the alkoxy groups.

Graphical abstract: Synthesis and structures of lithium alkoxytris(dimethylphenylsilyl)borates
Communication

Hydrogen-bridged bis(silylene) complexes of ruthenium and iron: synthesis, structures and multi-centre bonding interactions at the M–Si–H–Si four-membered ring

Ruthenium and iron complexes featuring a MSi2H four-centre bonding interaction were synthesized and the interaction was evaluated experimentally and theoretically.

Graphical abstract: Hydrogen-bridged bis(silylene) complexes of ruthenium and iron: synthesis, structures and multi-centre bonding interactions at the M–Si–H–Si four-membered ring
Paper

A Pt(0) complex with cyclic (alkyl)(amino)silylene and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligands: synthesis, molecular structure, and catalytic hydrosilylation activity

A platinum(0) complex bearing a cyclic (alkyl)(amino)silylene and a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVTMS) was synthesized and isolated in the form of colorless crystals.

Graphical abstract: A Pt(0) complex with cyclic (alkyl)(amino)silylene and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligands: synthesis, molecular structure, and catalytic hydrosilylation activity
Paper

Reactivity studies of silylene [PhC(NtBu)2](C5Me5)Si – reactions with [M(COD)Cl]2 (M = Rh(I), Ir(I)), S, Se, Te, and BH3

The reactivity of N-heterocyclic silylene [PhC(NtBu)2](C5Me5)Si towards main group elements and transition metals was evaluated.

Graphical abstract: Reactivity studies of silylene [PhC(NtBu)2](C5Me5)Si – reactions with [M(COD)Cl]2 (M = Rh(i), Ir(i)), S, Se, Te, and BH3
Paper

Molecular structures of various alkyldichlorosilanes in the solid state

A series of organodichlorosilanes RR′SiCl2 (R,R′ = (CH2)3; (CH2)4; (CH2)5; Me,Me; Me,H; Me,Cl) was studied by single-crystal X-ray diffraction analyses.

Graphical abstract: Molecular structures of various alkyldichlorosilanes in the solid state
Open Access Paper

Monolithic porous magnesium silicide

Macroporous magnesium silicide monoliths were prepared by a two-step magnesiothermic reaction starting from hierarchically structured silica with silicon as an intermediate step.

Graphical abstract: Monolithic porous magnesium silicide
Paper

A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes

Rh and Ir coordination of phosphines with 1 to 3 Si–H groups.

Graphical abstract: A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes
Paper

Radical cations of phenyl silatrane

Electrochemical oxidation of phenyl silatrane provides persistent radical cations with an unpaired electron mostly localized on the atrane nitrogen.

Graphical abstract: Radical cations of phenyl silatrane
Paper

(Oligo)aromatic species with one or two conjugated Si[double bond, length as m-dash]Si bonds: near-IR emission of anthracenyl-bridged tetrasiladiene

Si[double bond, length as m-dash]Si transfer to bulky (poly)aromatic substrates is described. Some products show intermolecular charge transfer bands and weak fluorescence.

Graphical abstract: (Oligo)aromatic species with one or two conjugated Si [[double bond, length as m-dash]] Si bonds: near-IR emission of anthracenyl-bridged tetrasiladiene
Paper

Borane-catalysed postpolymerisation modification of the Si–H bonds in poly(phenylsilane)

An unusually wide variety of new sidechains are introduced at a polysilane through chemoselective catalytic hydrosilation, heterodehydrocoupling, and demethanative coupling.

Graphical abstract: Borane-catalysed postpolymerisation modification of the Si–H bonds in poly(phenylsilane)
Open Access Paper

Flexible organofunctional aerogels

Flexible inorganic–organic silica aerogels based on methyltrimethoxysilane (MTMS, CH3Si(OCH3)3) can overcome the drawbacks of conventional silica aerogels by introducing high mechanical strength, elastic recovery and hydrophobicity to monolithic materials.

Graphical abstract: Flexible organofunctional aerogels
Paper

The thrombogenic activity of POSS silanols

In vitro studies into the interaction of polyhedral oligomeric silsesquioxane (POSS) trisilanols with porcine and human red blood cells (erythrocytes), and mouse fibroblasts with is reported.

Graphical abstract: The thrombogenic activity of POSS silanols
Paper

[PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules

Traditional electrophilic bromination follows long established “rules”: electron-withdrawing substituents cause bromination selective for meta positions, whereas electron-donating substituents favor ortho and para bromination.

Graphical abstract: [PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules
Open Access Paper

Synthesis and methane cracking activity of a silicon nitride supported vanadium nitride nanoparticle composite

Vanadium nitride–silicon nitride nanocomposites from triflate-catalysed co-ammonolysis are active for COx-free H2 production from methane.

Graphical abstract: Synthesis and methane cracking activity of a silicon nitride supported vanadium nitride nanoparticle composite
Paper

Asymmetric charge separation and recombination in symmetrically functionalized σ–π hybrid oligosilanes

The flexibility of σ-conjugated silanes presents new opportunities for controlling charge transfer via changes in molecular conformation.

Graphical abstract: Asymmetric charge separation and recombination in symmetrically functionalized σ–π hybrid oligosilanes
Paper

Reaction of the thermo-labile triazenide Na[tBu3SiNNNSiMe3] with CO2: formation of the imido carbonate (tBu3SiO)(Me3SiO)C[double bond, length as m-dash]N-SitBu3 and carbamine acid (tBu3SiO)CONH2

A one-pot synthesis of (tBu3SiO)(Me3SiO)C[double bond, length as m-dash]N-SitBu3 and (tBu3SiO)CONH2 was achieved by the reaction of Na[SitBu3] with Me3SiN3 and subsequent CO2 treatment.

Graphical abstract: Reaction of the thermo-labile triazenide Na[tBu3SiNNNSiMe3] with CO2: formation of the imido carbonate (tBu3SiO)(Me3SiO)C [[double bond, length as m-dash]] N-SitBu3 and carbamine acid (tBu3SiO)CONH2
Paper

Optical spectra, electronic structure and aromaticity of benzannulated N-heterocyclic carbene and its analogues of the type C6H4(NR)2E: (E = Si, Ge, Sn, Pb)

Aromaticity of carbene analogues of the type C6H4(NR)2E: (E = C–Pb) has been established by Raman, UV-vis, ISE, NICS and ACID methods.

Graphical abstract: Optical spectra, electronic structure and aromaticity of benzannulated N-heterocyclic carbene and its analogues of the type C6H4(NR)2E: (E = Si, Ge, Sn, Pb)
Paper

Diastereoselective silylene transfer reactions to chiral enantiopure alkenes: effects of ligand size and substrate bias

When silylene transfer reactions are irreversible, the steric hinderance of the alkene and ligands on the metal catalyst does not influence stereoselectivity, but when the reaction is reversible (above), silyene transfer reactions can be diastereoselective.

Graphical abstract: Diastereoselective silylene transfer reactions to chiral enantiopure alkenes: effects of ligand size and substrate bias
Paper

Controlled synthesis of cyclosiloxanes by NHC-catalyzed hydrolytic oxidation of dihydrosilanes

Hydrolytic oxidation of dihydrosilanes with water in acetonitrile with 0.1 mol% of NHC produced hydrogen gas and cyclosiloxanes in excellent yields.

Graphical abstract: Controlled synthesis of cyclosiloxanes by NHC-catalyzed hydrolytic oxidation of dihydrosilanes
From the themed collection: Dalton Transactions Inorganic Symposia
Paper

Syntheses of transition metal methoxysiloxides

The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes.

Graphical abstract: Syntheses of transition metal methoxysiloxides
Paper

Gold nanoparticles stabilized by cationic carbosilane dendrons: synthesis and biological properties

Water soluble gold nanoparticles have been isolated with pendant cationic carbosilane dendrons and their biological properties have been evaluated.

Graphical abstract: Gold nanoparticles stabilized by cationic carbosilane dendrons: synthesis and biological properties
Open Access Paper

A structural study of alkaline earth metal complexes with hybrid disila-crown ethers

A series of disila-crown ether complexes have been characterized by single crystal X-ray diffraction. The complex stability of different systems were studied by DFT calculations and proton NMR experiments.

Graphical abstract: A structural study of alkaline earth metal complexes with hybrid disila-crown ethers
Paper

Neutral six-coordinate bis(dithiocarbamato)silicon(IV) complexes with an SiCl2S4 skeleton

The first six-coordinate bis(dithiocarbamato)silicon(IV) complexes, compounds 3 and 4 with their unprecedented SiCl2S4 skeleton, were synthesised and structurally characterised.

Graphical abstract: Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton
25 items

About this collection

The chemistry of silicon continues to have wide-ranging impact in diverse arenas of science and technology, including medicine, materials, energy, and catalysis. Discoveries in fundamental aspects of silicon chemistry continue to contribute to long-standing applications such as those derived from silicon-based semiconductors, and promise to enable new technological advances. The goal of this issue is to showcase the diverse fundamental and applied science associated with silicon, and Dalton Transactions is an excellent venue to illustrate how these efforts are global in nature.

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