Low oxidation state and hydrido group 2 complexes: synthesis and applications in the activation of gaseous substrates

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5054 - 5082

Опубликована: Янв. 1, 2024

This review summarises advances in the chemistry of low-oxidation state and hydrido group 2 metal complexes, focussing on their use for reductive activation feed-stock gaseous small molecules, subsequent transformation into value added products.

Язык: Английский

---

The borderless world of chemical bonding across the van der Waals crust and the valence region

Chemical Science, Год журнала: 2023, Номер 14(42), С. 11647 - 11688

Опубликована: Янв. 1, 2023

The definition of the van der Waals crust as spherical section between atomic radius and an element is discussed a survey application penetration index two interacting atoms in wide variety covalent, polar, coordinative or noncovalent bonding situations presented. It shown that this newly defined parameter permits comparison pairs structural computational studies independently atom sizes.

Язык: Английский

---

A nucleophilic beryllyl complex via metathesis at [Be–Be]2+

Nature Chemistry, Год журнала: 2024, Номер 16(8), С. 1295 - 1300

Опубликована: Май 17, 2024

Owing to its high toxicity, the chemistry of element number four, beryllium, is poorly understood. However, as lightest elements provide basis for fundamental models chemical bonding, there a need greater insight into properties beryllium. In this context, homo-elemental Be-Be bond interest. Here ligand metathesis diberyllocene (1; CpBeBeCp)-a stable complex with bond-has been investigated. These studies yield two complexes bonds: Cp*BeBeCp (2) and [K{(HCDippN)

Язык: Английский

---

Formation, Structure and Reactivity of a Beryllium(0) Complex with Mg^δ+−Be^δ− Bond Polarization

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 31, 2024

Attempts to create a novel Mg-Be bond by reaction of [(

Язык: Английский

---

Heterobimetallic alkaline earth metal–metal bonding

Nature Synthesis, Год журнала: 2023, Номер 3(3), С. 368 - 377

Опубликована: Дек. 4, 2023

Язык: Английский

---

A lithium–aluminium heterobimetallic dimetallocene

Nature Chemistry, Год журнала: 2024, Номер 16(7), С. 1093 - 1100

Опубликована: Май 14, 2024

Abstract Homobimetallic dimetallocenes exhibiting two identical metal atoms sandwiched between η 5 bonded cyclopentadienyl rings is a narrow class of compounds, with representative examples being dizincocene and diberyllocene. Here we report the synthesis structural characterization heterobimetallic dimetallocene, accessible through heterocoupling lithium aluminylene fragments pentaisopropylcyclopentadienyl ligands. The Al–Li bond features high ionic character profits from attractive dispersion interactions isopropyl groups A key synthetic step isolation cyclopentadienylaluminylene monomer, which also enables this species. In addition to their authentication by single-crystal X-ray diffraction analysis, both compounds were characterized multinuclear NMR spectroscopy in solution solid state. Furthermore, reactivity studies lithium–aluminium dimetallocene an N-heterocyclic carbene different heteroallenes performed show that easily cleaved.

Язык: Английский

---

Borozenes: Benzene-Like Planar Aromatic Boron Clusters

Accounts of Chemical Research, Год журнала: 2024, Номер 57(16), С. 2428 - 2436

Опубликована: Авг. 3, 2024

ConspectusWith three valence electrons and four orbitals, boron (2s22p1) is an electron-deficient element, resulting in interesting chemical bonding structures both borane molecules bulk materials. The electron deficiency leads to sharing delocalization compounds allotropes, characterized by polyhedral cages, particular, the ubiquitous B12 icosahedral cage. During past two decades, of size-selected clusters have been elucidated via combined photoelectron spectroscopy theoretical investigations. Unlike materials, finite found possess 2D consisting B3 triangles, dotted with tetragonal, pentagonal, or hexagonal holes. discovery planar B36 cluster a central hole provided first experimental evidence for viability nanostructures (borophene), which synthesized on inert substrates. B7–, B8–, B9– were among few be investigated joint calculations, they all B atom inside Bn ring. Recently, B73– (C6v), B82– (D7h), (D8h) series closed-shell species shown similar π akin that C5H5–, C6H6, C7H7+ series, respectively, name "borozene" was coined highlight their analogy classical aromatic hydrocarbon molecules.Among borozenes, D7h unique its high stability originating from double aromaticity fact B7 ring has perfect size host atom. borozene realized experimentally variety MB8 M2B8 complexes. In observed stabilize rare valence-I oxidation state lanthanides LnB8– complexes, as well Cu2+ Cu2B8–. B6 too small atom, slight out-of-plane distortion. Interestingly, bowl-shaped coordination metal leading observation highly stable MB7 On other hand, B8 slightly large such low-lying low-symmetry isomer also exists B9–. Even though most are aromatic, B73–, B82–, borozenes special because symmetries prototypical compounds. This Account discusses recent advances investigations various It expected many new can designed may eventually synthesized.

Язык: Английский

---

CaY@C_2n: Exploring Molecular Qubits with Ca–Y Metal–Metal Bonds

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(35), С. 24310 - 24319

Опубликована: Авг. 21, 2024

Metal–metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects chemical bonds. bonds based on alkaline-earth (Ae) elements, especially heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 CaY@C2v(5)-C80, which contain unprecedented single-electron Ca–Y metal–metal These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, DFT calculations. The crystallographic study shows that Ca Y successfully encapsulated into carbon cage with a distance 3.691 Å. CW-EPR both CaY@C2v(5)-C80 exhibits doublet, suggesting presence an unpaired located between Y. combined experimental theoretical results confirm bond substantial covalent interaction, attributed significant overlap 4s4p orbitals 5s5p4d Furthermore, pulse EPR spectroscopy was used investigate quantum coherence spin within this bond. electron, its s orbital nature, effectively protected cage, resulting efficient suppression spin–lattice relaxation decoherence. behaves as qubit, displaying maximum decoherence time 7.74 μs at 40 K. This reveals Ae–rare-earth stabilized fullerene cages elucidates molecular qubit properties stemming from unique character, highlighting potential information processing applications.

Язык: Английский

---

On the nature and limits of alkaline earth–triel bonding

Chemical Science, Год журнала: 2024, Номер 15(37), С. 15377 - 15384

Опубликована: Янв. 1, 2024

The synthesis of a series isostructural organometallic complexes featuring Ae-Tr bonds (Ae = Be, Mg; Tr Al, Ga, In) has been investigated, and their electronic structures probed by quantum chemical calculations. This systematic study allows for comparison, not only the metal-metal bonding chemistries two lightest alkaline earth (Ae) elements, beryllium magnesium, but also three triel (Tr) aluminium, gallium, indium. Computational analyses (NBO, QTAIM, EDA-NOCV) reveal that Be-Tr is more covalent than Mg-Tr bonding. More strikingly, these calculations predict beryllium-indyl complex - first structurally characterised Be-In bond should act as source nucleophilic beryllium. confirmed experimentally its reactivity towards methyl iodide, which yields Be-Me functionality. By extension, electrophilic character centre in beryllium-gallyl contrasts with umpoled, behaviour both -indyl -aluminyl complexes.

Язык: Английский

---

Main group metal-mediated strategies for C–H and C–F bond activation and functionalisation of fluoroarenes

Chemical Science, Год журнала: 2023, Номер 14(42), С. 11617 - 11628

Опубликована: Янв. 1, 2023

This Perspective showcases recent advances on the use of specially designed main-group metal complexes to facilitate chemoselective C–H/C–F functionalisation fluoroarenes.

Язык: Английский

---