Ambiphilic Al−Cu Bonding

Hill, Michael S.; Liu, Han‐Ying; Schwamm, Ryan J.; McMullin, Claire L.; Mahon, Mary F.; Rajabi, Nasir A.

doi:10.1002/anie.202104658

Cited by 51 publications

(72 citation statements)

References 49 publications

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“…similar fashion, this reaction leads to the growth of an ew 13 CNMR signal at d C = 219.7 ppm, (cf. d C = 242.3 and 234.9 ppm for gold/copper compounds featuring M(CO 2 )Al units), [15,17] and the product in this case ( 7)c ould be crystallized from hexane,a llowing its identity to be definitively established by multinuclear NMR and analytical methods, and its connectivity to be determined crystallographically (Scheme 3a nd Figure 6). Thesolid-state structure of 7 confirms the regiochemistry of CO 2 insertion implied by spectroscopic measurements,that is,p roceeding via the formation of ZnÀCa nd AlÀOb onds, with the zinc centre of 6 formally acting as the nucleophilic partner.The role of steric factors in determining the nature of the insertion process also cannot be ruled out.…”

Section: Methodsmentioning

confidence: 97%

Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

et al. 2021

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Synthetic routes to lithium, magnesium, and zinc aluminyl complexes are reported, allowing for the first structural characterization of an unsupported lithium-aluminium bond. Crystallographic and quantum-chemical studies are consistent with the presence of ah ighly polar Li À Al interaction, characterized by al ow bond order and relatively little charge transfer from Al to Li. Comparison with magnesium and zinc aluminyl systems reveals changes to both the MÀAl bond and the (NON)Al fragment (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), consistent with am ore covalent character,w ith the latter complex being shown to react with CO 2 via ap athway that implies that the zinc centre acts as the nucleophilic partner.

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Section: Methodsmentioning

confidence: 97%

Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

et al. 2021

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“…In [a] In the case of compound 3 the Al-Al s-bonding interaction is primarily located in the HOMO-4;data given relate to this orbital. [15,17] and the product in this case ( 7)c ould be crystallized from hexane,a llowing its identity to be definitively established by multinuclear NMR and analytical methods, and its connectivity to be determined crystallographically (Scheme 3a nd Figure 6). Thesolid-state structure of 7 confirms the regiochemistry of CO 2 insertion implied by spectroscopic measurements,that is,p roceeding via the formation of ZnÀCa nd AlÀOb onds, with the zinc centre of 6 formally acting as the nucleophilic partner.The role of steric factors in determining the nature of the insertion process also cannot be ruled out.…”

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confidence: 99%

“…[9, 10e, 13, 14] Of systems reported to date,o nly two are accessible as separated ion pairs featuring the effectively "naked" aluminyl anion, with the K + cation having been sequestered by the use of ac ryptand or crown ether ligand. [10c,13] Cation exchange has been touched upon in the synthesis of aluminyl compounds featuring Mg, [9,10d] Ca, [10d] Au, [15] Y [16] or Cu [17] partners,but to our knowledge no other alkali metal aluminyl compounds have been reported.…”

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confidence: 99%

“…[15] More recently Hill and co-workers have used as imilar approach to differentiate between nucleophilic and electrophilic copper centres in copper aluminyl systems featuring different supporting ligand sets. [17] With this in mind, we set out to examine the reactivity of 6 towards similar probe molecules.…”

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confidence: 99%

“…d C = 219.9 and 220.9 ppm for gold and copper compounds featuring M{C(N i Pr) 2 }Al motifs). [15,17] In this case,h owever, the product could not be crystallized-potentially due to the prescence of excess carbodiimide-and so the corresponding reaction with carbon dioxide was targeted in order to provide easier purification and access to definitive structural data. In [a] In the case of compound 3 the Al-Al s-bonding interaction is primarily located in the HOMO-4;data given relate to this orbital.…”

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confidence: 99%

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Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

et al. 2021

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Synthetic routes to lithium, magnesium, and zinc aluminyl complexes are reported, allowing for the first structural characterization of an unsupported lithium–aluminium bond. Crystallographic and quantum‐chemical studies are consistent with the presence of a highly polar Li−Al interaction, characterized by a low bond order and relatively little charge transfer from Al to Li. Comparison with magnesium and zinc aluminyl systems reveals changes to both the M−Al bond and the (NON)Al fragment (where NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), consistent with a more covalent character, with the latter complex being shown to react with CO2 via a pathway that implies that the zinc centre acts as the nucleophilic partner.

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A Free Aluminylene with Diverse σ‐Donating and Doubly σ/π‐Accepting Ligand Features for Transition Metals**

Liu

Zhang

2021

Angewandte Chemie

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We report herein the synthesis,characterization, and coordination chemistry of af ree N-aluminylene,n amely ac arbazolylaluminylene 2b.T his species is prepared via ar eduction reaction of the corresponding carbazolyl aluminium diiodide.T he coordination behavior of 2b towards transition metal centers (W,C r) is shown to affordaseries of novel aluminylene complexes 3-6 with diverse coordination modes.W edemonstrate that the tri-active ambiphilic Al center in 2b can behave as:1 .as-donating and doubly p-accepting ligand;2 .a s-donating, s-accepting and p-accepting ligand; and 3. a s-donating and doubly s-accepting ligand. Additionally,w es how ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of 2b with IDippCuCl (IDipp = 1,3-bis(2,6diisopropylphenyl)imidazol-2-ylidene) show an unprecedented aluminylene-alumanyl transformation leading to ar are terminal Cu-alumanyl complex 8.The electronic structures of such complexes and the mechanism of the aluminylenealumanyl transformation are investigated through density functional theory (DFT) calculations.[**] Aprevious version of this manuscript has been deposited on apreprint server (https://chemrxiv.org/engage/chemrxiv/articledetails/61205bc21d1cc23402c90876).

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Ambiphilic Al−Cu Bonding

Cited by 51 publications

References 49 publications

Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds

A Free Aluminylene with Diverse σ‐Donating and Doubly σ/π‐Accepting Ligand Features for Transition Metals**

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