Access to FeII Bis(σ-B-H) Aminoborane Complexes through Protonation of a Borohydride Complex and Dehydrogenation of Amine-Boranes.

Herein, we report on the first synthesis and structural characterization of the iron based aminoborane complexes [Fe(PNP)(H)(η2 :η2 -H2 B=NR2 )]+ (R=H, Me). These species are formed upon protonation of the borohydride complex [Fe(PNP)(H)(η2 -BH4 )] by ammonium salts [NH2 R2 ]+ (R=H, Me). For R=Me, the reaction proceeds via the cationic dinuclear intermediate [{Fe(PNP)(H)}2 (μ2 ,η2 :η2 -BH4 )]+ . A mechanism for the reaction is proposed based on DFT calculations that also indicate the final aminoborane complex as the thermodynamic product. All complexes were characterized by NMR spectroscopy, HRMS, and X-ray crystallography.