Contemporary developments in transition metal boryl complexes: An overview

Kaur, Urminder; Saha, Koushik; Gayen, Sourav; Ghosh, Sundargopal

doi:10.1016/j.ccr.2021.214106

Cited by 30 publications

(27 citation statements)

References 165 publications

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“…We mention that the experimentally accessible coinage-metal–boryl complexes possess mainly acyclic (such as the very recent gold boryl complex bearing a boryl with two o -tolyl substituents) 18 or five-membered structures. 15 , 24 , 27 A comparative study of the electronic structure of boryl/aluminyl anions, including a systematic analysis of the structural and substituent effects, is currently under way in our laboratory.…”

Section: Introductionmentioning

confidence: 99%

“…It is worth reminding that the aluminyl and indyl ligands in complexes I Al and I In have been actually synthesized and characterized experimentally , and that similar heterocyclic structures appear to be reasonably accessible for Ga. Analogous boryl complex I B has not been included in this work since the constrained six-member heterocyclic ring structure ([B( Si NON)] − ) represents a poorly realistic model complex, not directly comparable to the aluminyl, gallyl, and indyl analogues. We mention that the experimentally accessible coinage-metal–boryl complexes possess mainly acyclic (such as the very recent gold boryl complex bearing a boryl with two o -tolyl substituents) or five-membered structures. ,, A comparative study of the electronic structure of boryl/aluminyl anions, including a systematic analysis of the structural and substituent effects, is currently under way in our laboratory.…”

Section: Introductionmentioning

confidence: 99%

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What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold–Aluminyl, −Gallyl, and −Indyl Complexes

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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Anionic aluminum(I) anions (“aluminyls”) are the most recent discovery along Group 13 anions, and the understanding of the unconventional reactivity they are able to induce at a coordinated metal site is at an early stage. A striking example is the efficient insertion of carbon dioxide into the Au–Al bond of a gold–aluminyl complex. The reaction occurs via a cooperative mechanism, with the gold–aluminum bond being the actual nucleophile and the Al site also behaving as an electrophile. In the complex, the Au–Al bond has been shown to be mainly of an electron-sharing nature, with the two metal fragments displaying a diradical-like reactivity with CO 2 . In this work, the analogous reactivity with isostructural Au–X complexes (X = Al, Ga, and In) is computationally explored. We demonstrate that a kinetically and thermodynamically favorable reactivity with CO 2 may only be expected for the gold–aluminyl complex. The Au–Al bond nature, which features the most (nonpolar) electron-sharing character among the Group 13 anions analyzed here, is responsible for its highest efficiency. The radical-like reactivity appears to be a key ingredient to stabilize the CO 2 insertion product. This investigation elucidates the special role of Al in these hetero-binuclear compounds, providing new insights into the peculiar electronic structure of aluminyls, which may help for the rational control of their unprecedented reactivity toward carbon dioxide.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold–Aluminyl, −Gallyl, and −Indyl Complexes

Sorbelli

Belpassi²,

Belanzoni

2022

Inorg. Chem.

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“…12–15 In this latter regard, the most significant activity has centred on the exploitation of boron-centred (boryl) moieties as strongly σ-donating ligands to transition metal (TM) centres and their attendant applications in synthesis and C–B bond-forming catalysis. 16–19…”

Section: Introductionmentioning

confidence: 99%

On the reactivity of Al-group 11 (Cu, Ag, Au) bonds

et al. 2022

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“…Green and sustainable chemistry is the key to overcoming the imminent challenges posed by global climate warming and the energy crisis. Earth-abundant metal complexes offer an inexpensive and sustainable alternative to the unsustainable use of precious metal catalysts in many organic transformations, especially on an industrial scale. − Although s-block alkaline-earth metals such as calcium and magnesium are among the most abundant metals in the Earth’s crust (heavier alkaline-earth calcium being the third most abundant metal), their application in catalysis is still underdeveloped compared with the extensive study of transition metals. This can primarily be attributed to their tendency to undergo Schlenk-type equilibrium.…”

Section: Introductionmentioning

confidence: 99%

Calcium-Catalyzed Hydroboration of Alkenes

Luo

Shi

Chen

et al. 2022

ACS Sustainable Chem. Eng.

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Earth-abundant group 2 metal complexes offer an inexpensive and sustainable alternative to precious transition metal catalysts in many synthetic scenarios. As such, calcium and magnesium catalysts have attracted ever increasing interest as viable replacements for traditional transition metalbased catalysts for alkene hydroboration. Herein, we report the alkaline-earth metal-catalyzed hydroboration of alkenes with HBpin using commercially available CaCl 2 , reusable MOF-Ca, and subvalent Mg(I) complexes as highly efficient catalysts. The simple air-and moisture-stable CaCl 2 and MOF-Ca catalytic systems both show high reactivity in the hydroboration of various alkenes to afford the anti-Markovnikov products in high yield and high regioselectivity under low catalyst loading (1−3 mol %) and almost solvent-free conditions. To the best of our knowledge, this is the first example of a main-group Ca-catalyzed hydroboration of alkenes, and it represents a potential pathway for the further discovery and application of inexpensive alkaline-earth metal-based catalysis.

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Contemporary developments in transition metal boryl complexes: An overview

Cited by 30 publications

References 165 publications

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold–Aluminyl, −Gallyl, and −Indyl Complexes

What Singles out Aluminyl Anions? A Comparative Computational Study of the Carbon Dioxide Insertion Reaction in Gold–Aluminyl, −Gallyl, and −Indyl Complexes

On the reactivity of Al-group 11 (Cu, Ag, Au) bonds

Calcium-Catalyzed Hydroboration of Alkenes

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