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

04 June 2025, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Heterometallic assemblies have been key in uncovering new modes of reactivity. Synergistic effects resulting from metals such as Al have garnered attention and inquiries regarding the electronic state of Al that influences reactivity of interest. Al and Al–H moieties are described to be capable of accessing a variety of states including sigma accepting alanes, sigma donating alanes, aluminyls, and aluminylenes. We report a NiAl cluster that features site-differentiating Al centers through Al–H addition, cooperative olefin insertion, and alkyl transfer, the latter of which represents elementary steps related to the “Nickel Effect”. Crystallographic and spectroscopic tools, including T1 studies, clearly demonstrate the site-differentiation of the three Al/Al–H centers.

Supplementary materials

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Supplementary Information
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Experimental procedures and NMR data for LH2, LAlH2, 1, and 1-D5 and X-ray crystallographic information, and di-merization trials for 1.
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CIF File
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Crystallographic Information File for Cluster 1.
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