Group 11 Bis(alumanyl)metallates DOI Creative Commons
Han‐Ying Liu, James A. Kenar, Samuel E. Neale

et al.

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Reactions of the coinage metal (CM) cyanides, CuCN, AgCN, or K[Au(CN)2], with [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp 2,6-i-Pr2C6H3) result in KCN metathesis and a series "alumina-Gilman" reagents, [({SiNDipp}Al)2CM]K (CM Cu, Ag, Au). The latter species may be isolated both charge-separated, [({SiNDipp}Al)2CM]−[K(THF)6]+, contact ion pair forms when crystallized presence absence THF. Computational analysis apportions high degree covalency to CM–Al bonding attribution an aluminum oxidation state that is best represented as Al(II). This inference supported by experimental observation THF activation, deduced from competitive single electron reduction group 11 center during synthesis bis(alumanyl)metalates. UV photolysis [({SiNDipp}Al)2Ag]K provided product 2-fold Al(II) radical addition benzene. also synthesized modification reaction gave rise initially identified cuprate product. intermediacy [{SiNDipp}Al•] radicals, which are proposed add benzene stepwise manner, situ recorded EPR spectra, simulated parameters have been assigned singly aluminated product, [{SiNDipp}Al(C6H6)•].

Language: Английский

On the nature and limits of alkaline earth–triel bonding DOI Creative Commons
Josef T. Boronski,

Liam P. Griffin,

Caroline Conder

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15377 - 15384

Published: Jan. 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.

Language: Английский

Citations

6
Reductive Coupling of Ketones: Contrasting the Reactivity of an Aluminyl and a Gallyl Anion DOI
Andrea O’Reilly, Richard Robson, Matthew J. Evans

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

The synthesis of a new potassium gallyl system, K[Ga(NON)] ([NON]2- = [O(SiMe2NDipp)2]2-, Dipp 2,6-iPr2C6H3), has been reported, and its reactivity toward variety ketones studied. is initially isolated as the contacted dimeric pair (CDP) [K{Ga(NON)}]2 but can be converted to monomeric ion (MIP) (NON)Ga-K(TMEDA)2 or separated (SIP) [K(222-crypt)][Ga(NON)] upon addition coordinating polydentate ligands. reaction CDP with two equivalents benzophenone 9-fluorenone per gallium center generates homocoupled pinacolate products. However, acetophenone forms 1,3-phenylethene-1-olate, which C-C couples second equivalent form an unprecedented 1,3-diphenylbutane-1,3-diolate. This contrasted analogous aluminyl [K{Al(NON)}]2, where preferential formation product observed under same conditions.

Language: Английский

Citations

0
Synthesis, Isolation, and Reactivity Studies of ‘Naked’ Acyclic Gallyl and Indyl Anions DOI Creative Commons
Debotra Sarkar, Petra Vasko,

Tihomir Gluharev

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 22, 2024

Abstract By exploiting the electronic capabilities of N‐heterocyclic boryloxy (NHBO) ligand, we have synthesized “naked” acyclic gallyl [Ga{OB(NDippCH) 2 } ] − and indyl [In{OB(NDippCH) anions (as their [K(2.2.2‐crypt)] + salts) through K abstraction from [KGa{OB(NDippCH) [KIn{OB(NDippCH) using 2.2.2‐crypt. These systems represent first O‐ligated gallyl/indyl systems, are ultimately accessed cyclopentadienyl Ga I /In precursors by substitution chemistry, display nucleophilic reactivity which is strongly influenced presence (or otherwise) counterion.

Language: Английский

Citations

2
Synthesis, Isolation, and Reactivity Studies of ‘Naked’ Acyclic Gallyl and Indyl Anions DOI Creative Commons
Debotra Sarkar, Petra Vasko,

Tihomir Gluharev

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 22, 2024

Abstract By exploiting the electronic capabilities of N‐heterocyclic boryloxy (NHBO) ligand, we have synthesized “naked” acyclic gallyl [Ga{OB(NDippCH) 2 } ] − and indyl [In{OB(NDippCH) anions (as their [K(2.2.2‐crypt)] + salts) through K abstraction from [KGa{OB(NDippCH) [KIn{OB(NDippCH) using 2.2.2‐crypt. These systems represent first O‐ligated gallyl/indyl systems, are ultimately accessed cyclopentadienyl Ga I /In precursors by substitution chemistry, display nucleophilic reactivity which is strongly influenced presence (or otherwise) counterion.

Language: Английский

Citations

1
Frustrated Lewis Pairs from Al–E{14} Bonds (E{14} = Ge, Sn, Pb) DOI

G. Smith,

Samuel E. Neale, Matthew J. Evans

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

The potassium aluminyl K[Al(NON)] ([NON]

Language: Английский

Citations

0
Group 11 Bis(alumanyl)metallates DOI Creative Commons
Han‐Ying Liu, James A. Kenar, Samuel E. Neale

et al.

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Reactions of the coinage metal (CM) cyanides, CuCN, AgCN, or K[Au(CN)2], with [{SiNDipp}AlK]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp 2,6-i-Pr2C6H3) result in KCN metathesis and a series "alumina-Gilman" reagents, [({SiNDipp}Al)2CM]K (CM Cu, Ag, Au). The latter species may be isolated both charge-separated, [({SiNDipp}Al)2CM]−[K(THF)6]+, contact ion pair forms when crystallized presence absence THF. Computational analysis apportions high degree covalency to CM–Al bonding attribution an aluminum oxidation state that is best represented as Al(II). This inference supported by experimental observation THF activation, deduced from competitive single electron reduction group 11 center during synthesis bis(alumanyl)metalates. UV photolysis [({SiNDipp}Al)2Ag]K provided product 2-fold Al(II) radical addition benzene. also synthesized modification reaction gave rise initially identified cuprate product. intermediacy [{SiNDipp}Al•] radicals, which are proposed add benzene stepwise manner, situ recorded EPR spectra, simulated parameters have been assigned singly aluminated product, [{SiNDipp}Al(C6H6)•].

Language: Английский

Citations

0