Diberyllocene, a stable compound of Be(I) with a Be–Be bond

Science, Год журнала: 2023, Номер 380(6650), С. 1147 - 1149

Опубликована: Июнь 15, 2023

The complex diberyllocene, CpBeBeCp (Cp, cyclopentadienyl anion), has been the subject of numerous chemical investigations over past five decades yet eluded experimental characterization. We report preparation and isolation compound by reduction beryllocene (BeCp2) with a dimeric magnesium(I) determination its structure in solid state means x-ray crystallography. Diberyllocene acts as reductant reactions that form beryllium-aluminum beryllium-zinc bonds. Quantum calculations indicate parallels between electronic diberyllocene simple homodiatomic species diberyllium (Be2).

Язык: Английский

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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

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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

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Alumanyl-Samarium(II): Synthesis, Characterization, and Reactivity Studies

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7204 - 7209

Опубликована: Март 5, 2024

Metal–metal bonded species involving lanthanides are intriguing but rare. The recently reported salt metathesis reaction of an Al anion and SmI2(thf)2 yields novel heterometallic compound possessing two distinctive Al–Sm bonds. Although the bonds were considerably long [3.518(1) 3.543(1) Å], DFT calculations indicated polar character Alδ−–Smδ+ This is first example lanthanide containing X-type ligands. Reactivity studies have demonstrated that introduction Sm(II) produces unique reactivity. with carbodiimide led to insertion into reductive coupling create oxalamidinate moiety, facilitated by Sm(II). Exposure Al–Sm–Al complex toward ethylene furnished a anionic aluminacyclopropane was spontaneously isomerized 1,4-dialuminacyclohexane derivative. important role facilitate ring expansion through alkyl-relay mechanism elucidated calculations.

Язык: Английский

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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

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Reversible [4 + 1] Cycloaddition of Arenes by a “Naked” Acyclic Aluminyl Compound

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 11792 - 11800

Опубликована: Апрель 16, 2024

The large steric profile of the N-heterocyclic boryloxy ligand, -OB(NDippCH)

Язык: Английский

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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

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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

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Recent progress in beryllium organometallic chemistry

Chemical Communications, Год журнала: 2024, Номер 60(13), С. 1663 - 1673

Опубликована: Янв. 1, 2024

Beryllium chemistry is on the rise. Examples of beryllium compounds with formal oxidation state 0, +1, cationic and neutral radical species, aromatic antiaromatic heterocycles a Be–Be bonded complex are proof to it.

Язык: Английский

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Alkaline earth metals: homometallic bonding

Dalton Transactions, Год журнала: 2023, Номер 53(1), С. 33 - 39

Опубликована: Ноя. 30, 2023

A discussion of the nature homometallic alkaline earth bonding is presented, recent synthetic advances are described, and future directions considered.

Язык: Английский

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