Synthesis of Bis(phosphino)silyl Pincer-Supported Iron Hydrides for the Catalytic Hydrogenation of Alkenes

The synthesis and characterization of Fe pincer complexes supported by a bis(phosphino)silyl (PSiP) ligand are described. While four-coordinate species of the type (PSiP)FeX (X = halide) proved challenging to access, examples of five-coordinate (PSiP)Fe(II) and (PSiP)Fe(I) species were prepared and crystallographically characterized. In studying the reactivity of such (PSiP)Fe precursors, a variety of iron hydride species were observed and characterized, and interconversion among such complexes facilitated by the coordination of N2 was noted. The structures and spectroscopic features of several such diamagnetic Fe(II) hydrides were elucidated, including that of a unique and highly stable η2-(Si–H)Fe(II) dihydride complex. A surrogate for a low coordinate (PSiP)FeH species in the form of its bis(dinitrogen) adduct was found to be an effective precatalyst for the direct hydrogenation of alkenes, including various mono- and disubstituted aliphatic alkenes, as well as a trisubstituted example. Esters and ethers were found to be well-tolerated by the catalyst, and alkyne hydrogenation was also demonstrated.