A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
The Dialuminene AriPr8AlAlAriPr8 (AriPr8 = C6H‐2,6‐(C6H2‐2,4,6‐iPr3)2‐3,5‐iPr2) (2024)

Lehmann, A., Queen, J. D., Roberts, C. J., Rissanen, K., Tuononen, H. M., & Power, P. P. (2024). The Dialuminene AriPr8AlAlAriPr8 (AriPr8 = C6H‐2,6‐(C6H2‐2,4,6‐iPr3)2‐3,5‐iPr2). Angewandte Chemie, Early online. https://doi.org/10.1002/anie.202412599

JYU-tekijät tai -toimittajat

Lehmann, Annika
Roberts, Christopher
Rissanen, Kari
Tuononen, Heikki

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Lehmann, Annika; Queen, Joshua D.; Roberts, Christopher J.; Rissanen, Kari; Tuononen, Heikki M.; Power, Philip P.

Lehti tai sarja: Angewandte Chemie

ISSN: 0044-8249

eISSN: 1521-3757

Julkaisuvuosi: 2024

Ilmestymispäivä: 19.08.2024

Volyymi: Early online

Kustantaja: Wiley

Julkaisumaa: Saksa

Julkaisun kieli: englanti

DOI: https://doi.org/10.1002/anie.202412599

Julkaisun avoin saatavuus: Ei avoin

Julkaisukanavan avoin saatavuus: 

Tiivistelmä

Careful analysis of the crystals formed in the reduction of AriPr8AlI2 (AriPr8 = C6H-2,6-(C6H2-2,4,6-iPr3)2-3,5-iPr2) with sodium on sodium chloride showed them to contain the long sought-after dialuminene AriPr8AlAlAriPr8 (1) that forms alongside the previously characterized alanediyl:AlAriPr8. The single crystal X-ray structure of 1 revealed a nearly planar, trans-bent C(ipso)AlAlC(ipso) core with an Al–Al distance of 2.648(2) Å. The molecular and electronic structure of 1 are consistent with a Al–Al double dative interaction augmented with diradical character and stabilized by dispersion interactions. Density functional theory calculations showed that the reactivity of:AlAriPr8 with dihydrogen involves 1, not:AlAriPr8, as the reactive species. In contrast, the reaction of:AlAriPr8 with ethylene gave two products, the 1,4-dialuminacyclohexane AriPr8Al(C2H4)2AlAriPr8 (2) and the aluminacyclopentane AriPr8Al(C4H8) (3), that can both form from the aluminacyclopropane intermediate AriPr8Al(C2H4). Although the [2+2+2] cycloaddition of 1 with two equivalents of ethylene was also calculated to be exergonic, it is likely to be kinetically blocked by the numerous isopropyl substituents surrounding the Al–Al bond. Attempts to fine-tune the steric bulk of the terphenyl ligand to allow stronger Al–Al bonding were unsuccessful, leading to the isolation of the sodium salt of a cyclotrialuminene, Na2[AlAriPr6]3 (4), instead of AriPr6AlAlAriPr6.

YSO-asiasanat: organometalliyhdisteet; alumiini; kiteet; kemialliset sidokset; tiheysfunktionaaliteoria

Vapaat asiasanat: main group elements; aluminum; multiple bonds; reaction mechanisms; density functional calculations

Liittyvät organisaatiot

Hankkeet, joissa julkaisu on tehty

OKM-raportointi: Kyllä

VIRTA-lähetysvuosi: 2024

Alustava JUFO-taso: 3