Carbon group ≈ Carbon group
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Nucleophilic Substitution (S<sub>N</sub>2): Dependence on Nucleophile, Leaving Group, Central Atom, Substituents, and Solvent Open
The reaction potential energy surface (PES), and thus the mechanism of bimolecular nucleophilic substitution (S N 2), depends profoundly on the nature of the nucleophile and leaving group, but also on the central, electrophilic atom, its s…
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Long‐Lived Radicals of the Heavier Group 15 Elements Arsenic, Antimony, and Bismuth Open
The syntheses and properties of long‐lived arsenic, antimony, and bismuth‐centered radicals are reviewed. In contrast to the rich phosphorus‐based radical chemistry, that of the heavier congeners is far less advanced, which can be attribut…
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Pyramidanes: The Covalent Form of the Ionic Compounds Open
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Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands Open
Interactions between the uranyl oxo atom and group 14 metal cations in macrocyclic Pacman complexes depend on both molecular cleft constraints and the fifth equatorial ligand of the uranyl.
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Transition-metal Complexes with Triple Bonds to Si, Ge, Sn, and Pb and Relevant Complexes Open
Transition-metal complexes featuring triple bonds to heavier Group 14 elements (Si, Ge, Sn, and Pb), which have long been synthetic challenges in organometallic chemistry, have been synthesized in the last few decades. In this highlight, s…
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Synthesis of Low‐Valent Dinuclear Group 14 Compounds with Element–Element Bonds by Transylidation Open
Dinuclear low‐valent compounds of the heavy main group elements are rare species owing to their intrinsic reactivity. However, they represent desirable target molecules due to their unusual bonding situations as well as applications in bon…
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Precious and structural metals on asteroids Open
Metals and metallic elements in silicate/oxide form are abundant in asteroid materials and are often touted as a valuable space resource that can be returned to Earth or used in space. However, the data that come along with these claims ar…
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Cleavage of Ge–Ge and Sn–Sn Triple Bonds in Heavy Group 14 Element Alkyne Analogues (EAr<sup>iPr<sub>4</sub></sup>)<sub>2</sub> (E = Ge, Sn; Ar<sup>iPr<sub>4</sub></sup> = C<sub>6</sub>H<sub>3</sub>-2,6(C<sub>6</sub>H<sub>3</sub>-2,6-<sup>i</sup>Pr<sub>2</sub>)<sub>2</sub>) by Reaction with Group 6 Carbonyls Open
The reactions of heavier group 14 element alkyne analogues (EAriPr4)2 (E = Ge, Sn; AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) with the group 6 transition-metal carbonyls M(CO)6 (M = Cr, Mo, W) under UV irradiation resulted in the cleavage of the …
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Exploring benzylic <i>gem</i>-C(sp<sup>3</sup>)–boron–silicon and boron–tin centers as a synthetic platform Open
This work explores divergent reactivity of the benzylic gem-boron–silicon and boron–tin double nucleophiles, including the arylation of the C–B bond with Ar–Cl, along with a complementary oxidative λ3-iodane-guided arylation of the C–Si/Sn…
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Germanium- and tin-bridged diazulenylmethyl cations: effects of group 14 elements on the structure and properties of π-extended cations Open
Germanium- and tin-bridged diazulenylmethyl cations were synthesized, where the heavier elements increased their chemical stability, and affected the J-type aggregated absorption and fluorescence properties relative to those of the silicon…
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Complexes of adamantane‐based group 13 Lewis acids and superacids: Bonding analysis and thermodynamics of hydrogen splitting Open
The electronic structure and chemical bonding in donor–acceptor complexes formed by group 13 element adamantane and perfluorinated adamantane derivatives EC 9 R′ 15 (E = B, Al; R′ = H, F) with Lewis bases XR 3 and XC 9 H 15 (X = N, P; R= H…
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A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene Open
Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Herein, we report the synthesis of a silylene-stabilized ditin(0) complex ( 2 ) by reduction of a silylene-supported dibromostannylene ( 1 ) with 1 …
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Group 13 exchange and transborylation in catalysis Open
Catalysis is dominated by the use of rare and potentially toxic transition metals. The main group offers a potentially sustainable alternative for catalysis, due to the generally higher abundance and lower toxicity of these elements. Group…
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A Genuine Stannylone with a Monoatomic Two‐Coordinate Tin(0) Atom Supported by a Bis(silylene) Ligand Open
The monoatomic zero‐valent tin complex (stannylone) {[Si II (Xant)Si II ]Sn 0 } 5 stabilized by a bis(silylene)xanthene ligand, [Si II (Xant)Si II =PhC(NtBu) 2 Si(Xant)Si(NtBu) 2 CPh], and its bis‐tetracarbonyliron complex {[Si II (Xant)Si…
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Recent progress in the chemistry of heavy aromatics Open
The aromaticity and synthetic application of "heavy benzenes", i.e., benzenes containing a heavier Group 14 element (Si, Ge, Sn, and Pb) in place of skeletal carbon, have been the targets of many theoretical and synthetic studies. Although…
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Dialumene as a Dimeric or Monomeric Al Synthon for C–F Activation in Monofluorobenzene Open
The activation of C-F bonds has long been regarded as the subject of research in organometallic chemistry, given their synthetic relevance and the fact that fluorine is the most abundant halogen in the Earth's crust. However, C-F bond acti…
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<i>In situ ortho</i>-lithiation/functionalization of pentafluorosulfanyl arenes Open
A general method for ortho -functionalization of pentafluorosulfanyl arenes has been developed.
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Low Valent N‐Coordinated Cations and Dications of Heavier Group 14 Elements: Lewis Acids or Bases? Open
Low‐valent N‐coordinated cations and dications of heavier group 14 elements are of great interest in recent years. Their unique electronic structure gives them an ambiphilic character, as they contain both a lone electron pair and an empty…
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A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl Open
The Fischer carbene synthesis, involving the conversion of a transition metal (TM)-bound CO ligand to a carbene ligand of the form [=C(OR’)R] (R, R’ = organyl groups), is one of the seminal reactions in the history of organometallic chemis…
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Functional polymer materials containing heavy group‐14 elements focusing on germanium and tin Open
In this review, the synthesis, functions, and applications of the polymers containing germanium and tin, which are heavy group 14 elements, in their polymer frameworks are summarized. Germanium and tin can form similar skeletal structures …
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Crystalline Germanium(I) and Tin(I) Centered Radical Anions Open
An isostructural series of heavy Group 14 E(I) radical anions (Ge, Sn, Pb), stabilized by a bulky xanthene‐based diamido ligand are reported. The radical anions were synthesised by the one‐electron reduction of their corresponding E(II) pr…
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Crystal structure of a 1,1-dibutyl-1<i>H</i>,3<i>H</i>-naphtho[1,8-<i>cd</i>][1,2,6]oxastannaborinin-3-ol Open
The title oxastannaborininol compound, [Sn(C 4 H 9 ) 2 (C 10 H 7 BO 2 )], has been synthesized and crystallized. While heterocycles containing a C–O–B group are common, heterocycles containing an E –O–B unit, where E is an element of the c…
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Cage‐size effects on the encapsulation of <span>P<sub>2</sub></span> by fullerenes Open
The classic pnictogen dichotomy stands for the great contrast between triply bonding very stable N 2 molecules and its heavier congeners, which appear as dimers or oligomers. A banner example involves phosphorus as it occurs in nature as P…
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Synthesis and Thermal Investigations of Eleven-Membered Ring Systems Containing One of the Heavier Group 14 Element Atoms Si, Ge, and Sn Open
Unique eleven-membered rings containing silicon, germanium, and tin were synthesized in good yields by the reactions of the corresponding 1,2-bis((2-bromothiophen-3-yl)methoxy)benzenes with (C6H5)2ECl2 where E = Sn, Ge, Si. The Sn and Ge c…
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The Reduction of Metallabenzenes: Different Scenarios Highly Dependent on the Central Group 14 Elements, Si vs. Ge Open
In order to synthesize a silabenzenyl anion, in which the anionic carbon atom of a phenyl anion was replaced with a silicon atom, the reductive dearylation reaction of 1‐Tbt‐2‐ tert ‐butyl‐silabenzene (Tbt=2,4,6‐tris[bis(trimethylsilyl)met…
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Computational Density Functional Theory Investigation of Stability and Electronic Structures on Boron Nitride Systems Doped with/without Group IV Elements Open
In this paper, the stability as well as electronic structures of pure and group IV-substituted boron nitride (BN) cluster systems were investigated using Density Functional Theory (DFT) method. The results obtained from the DFT calculation…
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Trends in the Reactivity of Pentacyclic Ether Derivatives on Silicon and Germanium Surfaces Revealed by Energy Decomposition Analysis for Extended Systems Open
We analyze the adsorption and ring‐opening reaction of pentacyclic chalcogen alkyls with chalcogen atoms ranging from oxygen to tellurium using computational analysis. Thus extends our previous investigation of THF on silicon towards germa…
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Main Group Metal Complexes of Si, Ge and Al with an Unsymmetrical N,N’‐Substituted Diamide Ligand Open
Unsymmetrically N , N ’‐substituted metal amides of silicon, germanium and aluminium were synthesized starting from N ‐ethyl‐2‐( n ‐propylaminomethyl)phenylamine ( 1 , Et, n Pr‐ampaH 2 ). Reaction of the dilithium compound of 1 with SiCl 4…
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Frontispiece: Pentafluoroethylated Compounds of Silicon, Germanium and Tin Open
The introduction of electron-withdrawing pentafluoroethyl groups into organosilicon, organogermanium and organotin compounds by the treatment of organo-element halides with LiC2F5 creates a pronounced electron-deficiency at the central ato…
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Elusive group 14 elemental species stabilized by amidinato silylenes Open
This thesis describes the synthesis and isolation of a series of Group 14 elemental clusters bearing challenging and unique structural characteristics, all stabilized by an amidinato silylene ligand system. In Chapter 2, the synthesis of a…