Themed collection Frontiers in Molecular Main Group Chemistry
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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.
Chem. Commun., 2012,48, 10161-10161
https://doi.org/10.1039/C2CC90309A
Molecular early main group metal hydrides: synthetic challenge, structures and applications
Ligand-stabilized early main group metal hydride clusters.
Chem. Commun., 2012,48, 11165-11177
https://doi.org/10.1039/C2CC33478J
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.
Chem. Commun., 2012,48, 9559-9573
https://doi.org/10.1039/C2CC33221C
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.
Chem. Commun., 2012,48, 8617-8624
https://doi.org/10.1039/C2CC33015F
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.
Chem. Commun., 2012,48, 2169-2179
https://doi.org/10.1039/C2CC17449A
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.
Chem. Commun., 2012,48, 11295-11297
https://doi.org/10.1039/C2CC35318K
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.
Chem. Commun., 2012,48, 9616-9618
https://doi.org/10.1039/C2CC33300G
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.
Chem. Commun., 2012,48, 9385-9387
https://doi.org/10.1039/C2CC34860H
[(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).
Chem. Commun., 2012,48, 8676-8678
https://doi.org/10.1039/C2CC33652A
Synthesis of a stable 1,2-bis(ferrocenyl)diphosphene
A novel d–π electron system: 1,2-bis(ferrocenyl)diphosphene.
Chem. Commun., 2012,48, 8562-8564
https://doi.org/10.1039/C2CC33277A
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.
Chem. Commun., 2012,48, 8398-8400
https://doi.org/10.1039/C2CC33883A
Donor–acceptor stabilized silaformyl chloride
Silicon analogue of the formyl chloride, silaformyl chloride IPr·SiH(Cl)O·B(C6F5)3 (IPr = 1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene) was stabilized by Lewis donor–acceptor ligands.
Chem. Commun., 2012,48, 8186-8188
https://doi.org/10.1039/C2CC32887A
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.
Chem. Commun., 2012,48, 8096-8098
https://doi.org/10.1039/C2CC33361A
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.
Chem. Commun., 2012,48, 7922-7924
https://doi.org/10.1039/C2CC33206J
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.
Chem. Commun., 2012,48, 7820-7822
https://doi.org/10.1039/C2CC33911K
Synthesis and reactivity of cationic ruthenium germylene complexes [Cp*(PiPr3)RuH2(
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.
Chem. Commun., 2012,48, 7690-7692
https://doi.org/10.1039/C2CC32840B
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.
Chem. Commun., 2012,48, 7720-7722
https://doi.org/10.1039/C2CC32263C
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+.
Chem. Commun., 2012,48, 7589-7591
https://doi.org/10.1039/C2CC32605A
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.
Chem. Commun., 2012,48, 7359-7361
https://doi.org/10.1039/C2CC33082B
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.
Chem. Commun., 2012,48, 7262-7264
https://doi.org/10.1039/C2CC32690F
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.
Chem. Commun., 2012,48, 7212-7214
https://doi.org/10.1039/C2CC32727A
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.
Chem. Commun., 2012,48, 7185-7187
https://doi.org/10.1039/C2CC32696E
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.
Chem. Commun., 2012,48, 7094-7096
https://doi.org/10.1039/C2CC32790B
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.
Chem. Commun., 2012,48, 6984-6986
https://doi.org/10.1039/C2CC32615A
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.
Chem. Commun., 2012,48, 6930-6932
https://doi.org/10.1039/C2CC33059H
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.
Chem. Commun., 2012,48, 6803-6805
https://doi.org/10.1039/C2CC33045H
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.
Chem. Commun., 2012,48, 6595-6597
https://doi.org/10.1039/C2CC33047D
Rhenium complexes bearing phosphole –pyridine 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.
Chem. Commun., 2012,48, 6705-6707
https://doi.org/10.1039/C2CC32542J
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.
Chem. Commun., 2012,48, 6346-6348
https://doi.org/10.1039/C2CC32809G
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.
Chem. Commun., 2012,48, 6100-6102
https://doi.org/10.1039/C2CC32244G
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.
Chem. Commun., 2012,48, 5986-5988
https://doi.org/10.1039/C2CC31851B
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).
Chem. Commun., 2012,48, 5886-5888
https://doi.org/10.1039/C2CC32256K
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.
Chem. Commun., 2012,48, 5769-5771
https://doi.org/10.1039/C2CC31758C
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).
Chem. Commun., 2012,48, 5277-5279
https://doi.org/10.1039/C2CC31671D
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).
Chem. Commun., 2012,48, 4561-4563
https://doi.org/10.1039/C2CC31041D
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.
Chem. Commun., 2012,48, 4567-4569
https://doi.org/10.1039/C2CC30565H
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.
Chem. Commun., 2012,48, 4495-4497
https://doi.org/10.1039/C2CC30399J
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).
Chem. Commun., 2012,48, 2504-2506
https://doi.org/10.1039/C2CC18086C
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.
Chem. Commun., 2012,48, 1985-1987
https://doi.org/10.1039/C2CC16959B
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.
Chem. Commun., 2012,48, 1308-1310
https://doi.org/10.1039/C2CC17101E
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.