Reversible Dihydrogen Activation by Reduced Aryl Boranes as Main-Group Ambiphiles
作者： Esther von Grotthuss , Martin Diefenbach , Michael Bolte , Hans-Wolfram Lerner , Max C. Holthausen
关键词: Homolysis 、 Aryl 、 Ion 、 Frustrated Lewis pair 、 Chemistry 、 Reaction rate 、 Medicinal chemistry 、 Boron 、 Reactivity (chemistry) 、 Boranes 、 Inorganic chemistry
摘要: A new approach to main-group H2 activation combining concepts of transition-metal and frustrated Lewis pair chemistry is reported. Ambiphilic, metal-like reactivity toward can be conferred 9,10-dihydro-9,10-diboraanthracene (DBA) acceptors by the injection two electrons. The resulting [DBA]2− ions cleave H−H bond with formation hydridoborates under moderate conditions (T=50–100 °C; p<1 atm). Depending on boron-bonded substituents R, addition either reversible (R=C≡CtBu) or irreversible (R=H). reaction rate strongly influenced nature coordination behavior countercation (Li+ slower than K+). Quantum-chemical calculations support experimental observations suggest a concerted, homolytic across both boron atoms. As proven successful conversion Me3SiCl into Me3SiH, system Li2[DBA]/H2 appears generally relevant for hydrogenation element–halide bonds.
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