Gorgas Nikolaus, Stöger Berthold, Veiros Luis F, Kirchner Karl
Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163-AC, 1060, Wien, Austria.
X-Ray Center, Vienna University of Technology, Getreidemarkt 9, A-1060, Wien, Austria.
Angew Chem Int Ed Engl. 2019 Sep 23;58(39):13874-13879. doi: 10.1002/anie.201906971. Epub 2019 Aug 19.
Herein, we report on the first synthesis and structural characterization of the iron based aminoborane complexes [Fe(PNP)(H)(η :η -H B=NR )] (R=H, Me). These species are formed upon protonation of the borohydride complex [Fe(PNP)(H)(η -BH )] by ammonium salts [NH R ] (R=H, Me). For R=Me, the reaction proceeds via the cationic dinuclear intermediate [{Fe(PNP)(H)} (μ ,η :η -BH )] . 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.
在此，我们报道了铁基氨基硼烷配合物[Fe(PNP)(H)(η:η -H₂B=NR₂)]（R = H，Me）的首次合成及结构表征。这些物种是通过硼氢化物配合物[Fe(PNP)(H)(η²-BH₄)]与铵盐[NH₄R]（R = H，Me）质子化反应形成的。当R = Me时，反应通过阳离子双核中间体[{Fe(PNP)(H)}₂(μ,η²:η² -BH₄)]进行。基于密度泛函理论（DFT）计算提出了反应机理，该计算还表明最终的氨基硼烷配合物是热力学产物。所有配合物均通过核磁共振光谱（NMR）、高分辨质谱（HRMS）和X射线晶体学进行了表征。
