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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Access to a Labile Monomeric Magnesium Radical by Ball‐Milling

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(15)

Опубликована: Фев. 2, 2022

In order to isolate a monometallic Mg radical, the precursor (Am)MgI⋅(CAAC) (1) was prepared (Am=tBuC(N-DIPP)

Язык: Английский

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Synthesis and reactivity of low-oxidation-state alkaline earth metal complexes

Nature Synthesis, Год журнала: 2022, Номер 1(6), С. 439 - 448

Опубликована: Июнь 2, 2022

Язык: Английский

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Handling Beryllium, the Safe Way

ACS Chemical Health & Safety, Год журнала: 2023, Номер 30(2), С. 36 - 43

Опубликована: Март 9, 2023

This paper discusses the legislative response to handling beryllium and its compounds as well administrative regulations resulting from their classification potential human carcinogens. We describe necessary technical, organizational, personal safety measures comply with worker protection legislation ensure safe work compounds. conclude detailed solutions problems arising health hazards of beryllium.

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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Tuning the Selectivity of P4 Reduction at Alkaline-Earth Metal Centres

Chemical Science, Год журнала: 2025, Номер 16(10), С. 4528 - 4536

Опубликована: Янв. 1, 2025

Reduction of P4 with β-diketiminate MgI complexes, (BDI)MgMg(BDI), depends strongly on the bulk ligand. Whereas superbulky BDI ligands gave selective reduction to 2- in a butterfly conformation, less bulky ligand various products among which P8 4- had realgar-type structure. The selectivity can also be controlled by metal choice. CaI synthons general type (BDI*)Ca-X-Ca(BDI*) BDI* is and X bridging dianion (C6H6 < p-xylene2- N2 2-) led very common, stable Zintl anion P7 3-. Monitoring this process 31P NMR shows that cyclo-P4 an intermediate en route Conversion rates increase increasing reducing power: = C6H6 2-. A complex weakly DBA2- (DBA 9,10-dimethyl-diboraanthracene). DBA inhibits P4-to-P7 conversion, most likely capturing electron needed for further radical processes. Experimental investigations are supported crystal structure determinations computational DFT study nature metal-P4 bonding (covalent or ionic) determines preference formation butterfly-shaped planar 6π-electron aromatic

Язык: Английский

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Reductive Dimerization of CO by a Na/Mg(I) Diamide

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(42), С. 17851 - 17856

Опубликована: Окт. 15, 2021

Sodium reduction of [{SiNDipp}Mg] [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp 2,6-i-Pr2C6H3] provides the Mg(I) species, [{SiNDipp}MgNa]2, in which long Mg–Mg bond (>3.2 Å) is augmented by persistent Na–aryl interactions. Computational assessment indicates that this molecule best considered to comprise a contiguous tetrametallic core, viewpoint borne out its reaction with CO, results ethynediolate formation mediated dissimilar metal centers.

Язык: Английский

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The oxidation state in low-valent beryllium and magnesium compounds

Chemical Science, Год журнала: 2022, Номер 13(22), С. 6583 - 6591

Опубликована: Янв. 1, 2022

Low-valent group 2 (E = Be and Mg) stabilized compounds have been long synthetically pursued. Here we discuss the electronic structure of a series Lewis base-stabilized Mg compounds. Despite accepted zero(0) oxidation state nature elements some recent experimentally accomplished species, analysis multireference wavefunctions provides compelling evidence for strong diradical character with an +2. Thus, elaborate on distinction between description as donor-acceptor interaction L(0) ⇆ E(0) ⇄ internally oxidized situation, better interpreted L(-1) → E(+2) ← species. The examples rely strengthened bonds by increasing π-acidity ligand; avoiding this could lead to unprecedented low-oxidation state.

Язык: Английский

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Alkaline‐Earth Metal Mediated Benzene‐to‐Biphenyl Coupling

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 25, 2022

Complex [(DIPeP BDI)Ca]2 (C6 H6 ), with a C6 H62- dianion bridging two Ca2+ ions, reacts benzene to yield (biphenyl) biphenyl2- (DIPeP BDI=HC[C(Me)N-DIPeP]2 ; DIPeP=2,6-CH(Et)2 -phenyl). The biphenyl complex was also prepared by reacting ) or reduction of BDI)CaI]2 KC8 in presence biphenyl. Benzene-benzene coupling observed when the deep purple product ball-milling [(DIPP BDI)CaI(THF)]2 K/KI extracted (DIPP=2,6-CH(Me)2 -phenyl) giving crystalline BDI)Ca(THF)]2 (52 % yield). Reduction BDI)SrI]2 gave highly labile BDI)Sr]2 as black powder (61 yield) which rapidly and selectively (biphenyl). DFT calculations show that most likely route for formation is pathway attacks neutral benzene. This facilitated metal-benzene coordination.

Язык: Английский

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Beryllium-centred C–H activation of benzene

Chemical Communications, Год журнала: 2023, Номер 59(11), С. 1453 - 1456

Опубликована: Янв. 1, 2023

Reaction of BeCl2 with the dilithium diamide, [{SiNDipp}Li2] ({SiNDipp} = {CH2SiMe2NDipp}2), provides dimeric chloroberyllate, [{SiNDippBeCl}Li]2, en route to 2-coordinate beryllium amide, [SiNDippBe]. Lithium or sodium reduction [SiNDippBe] in benzene, relevant organoberyllate products, [{SiNDippBePh}M] (M Li Na), via presumed intermediacy transient Be(I) radicals.

Язык: Английский

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