The Dialuminene AriPr8AlAlAriPr8 (AriPr8 = C6H‐2,6‐(C6H2‐2,4,6‐iPr3)2‐3,5‐iPr2)
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
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2024Copyright
© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH
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.
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The content of the publication reflects only the author’s view. The funder is not responsible for any use that may be made of the information it contains.
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We thank the National Science Foundation (CHE-2152760 andCHE-1531193) for supporting this work. This project received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (GrantNo. 772510 to H.M.T.). We thank Dr. James C. Fettinger forcollecting the X-ray data.License
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