A Ni–Al Hydride Cluster Bearing Site-Differentiated Al Centers: Demonstration of Olefin Insertion and Alkyl Transfer

Authors

• Jordan R. Gipper
• Sergio Gonzalez-Eymard, The University of Texas Rio Grande Valley
• Julia Abdoullaeva
• Marco Caricato
• Manar M. Shoshani

Document Type

Article

Publication Date

11-3-2025

Abstract

Heterometallic assemblies have been key in uncovering new modes of reactivity, with synergistic effects resulting from main-group metals such as Al drawing particular attention given the diverse ligand modalities accessible to aluminum. Utilizing a reducing Al-dihydride metalloligand LAlH₂ and bis (1,5-cyclooctadiene)nickel(0), we report cluster 1, [LNiAl]₃H₅R (R = 4-cyclooctenyl). The cluster core features Al/Al–H moieties asymmetrically capping a Ni₃ plane and coordinating to a Ni–Ni edge. The Al centers display electronically differentiating sites through Al–H addition, olefin insertion, and alkyl transfer. Crystallographic, DFT, and spectroscopic tools establish the presence of three distinct Al centers that adopt sigma-donating alane, sigma-accepting alane, and nonalane character.

Recommended Citation

Gipper, Jordan R., Sergio Gonzalez-Eymard, Julia Abdoullaeva, Marco Caricato, and Manar M. Shoshani. "A Ni–Al Hydride Cluster Bearing Site-Differentiated Al Centers: Demonstration of Olefin Insertion and Alkyl Transfer." Inorganic Chemistry 64, no. 43 (2025): 21317-21322. https://doi.org/10.1021/acs.inorgchem.5c02694

Publication Title

Inorganic Chemistry

DOI

10.1021/acs.inorgchem.5c02694