Access to Fe^II Bis(σ‐B−H) Aminoborane Complexes through Protonation of a Borohydride Complex and Dehydrogenation of Amine‐Boranes

Abstract

Herein, we report on the first synthesis and structural characterization of the iron based aminoborane complexes [Fe(PNP)(H)(h 2 :h 2 -H 2 B=NR 2 )] + (R = H, Me). These species are formed upon protonation of the borohydride complex [Fe(PNP)(H)(h 2 -BH 4 )] by ammonium salts [NH 2 R 2 ] + (R = H, Me). ForR = Me,t he reaction proceeds via the cationic dinuclear intermediate [{Fe(PNP)(H)} 2 (m 2 ,h 2 :h 2 -BH 4 )] + .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 characterizedb yN MR spectroscopy, HRMS,a nd X-rayc rystallography.Scheme 1. Synthesis of complexes 2, 3,a nd 4.

Using electrospray ionization‐tandem mass spectrometry to explore formation and gas‐phase chemistry of silver nanoclusters generated from the reaction of silver salts with NaBH4 in the presence of bis(diphenylarsino)methane

“…This mode of BH 4 − has been observed in structurally characterized monocationic dimers of Fe, Cu, and Pd. [53][54][55] Computations suggest formation of this isomer relative to 16,18 In each case, the phosphine ligands were replaced by arsine ligands and then reoptimized. S29).…”