Iron-Mediated Si-H Bond Activation: Synthesis, Characterization and Spectral Properties of a Series of FeII(H)(SiR3)(dmpe)2 Complexes.

Synthesis and structural characterization of a series of iron(II) silyl hydrides stabilized by a bisphosphine ligand are discussed. FeII(H)(SiR3)(dmpe)2 compounds were formed by insertion of in situ generated Fe0(dmpe)2 in the presence of Si-H partners (R3SiH = PhSiH3, Ph2SiH2, and Ph3SiH). Multinuclear NMR monitoring (1H, 31P, 29Si) demonstrated a strong preference for the cis configuration regardless of the silicon substituents, a tendency mirrored by DFT calculations, which originates from the strong trans influence of the silyl ligands, making those compounds rather unusual in the family of octahedral ferrous hydrides. Stoichiometric reactivity of the compounds toward organic electrophiles and proton sources were investigated.