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

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.