Synthesis and characterization of NiAl-hydride heterometallics: perturbing electron density within Al-H-Ni subunits.

Heterometallic hydride complexes are of growing interest due to their potential to contribute to highly active insertion-based catalysis; however, methods to modulate electron density within this class of molecules are underexplored. Addition of ancillary ligands to heterotrimetallic NiAlH species (1) results in the formation of heterobimetallic NiAl-hydride complexes with varying phosphine donors (2-(L)2). Incorporation of sigma donating ancillary ligands of increasing strength led to contractions of the Ni-Al distances correlated to a strengthening of a back donation interaction to the Al-H sigma antibonding orbital, most prominently present in 2-(PMe3)2.