Stoichiometric reactions and catalytic dehydrogenations of amine–boranes with calcium aryloxide

Xizhou Zheng, Jiasu Huang, Yingming Yao ^*（姚英明） and Xin Xu ^*（徐信）

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.

Chem. Commun., 2019, 55, 9152--9155

Catalysis with the main-group metal calcium conventionally relies on σ-bond metathesis to initiate the reactions. Here, we report a calcium aryloxide based on the tridentate β-diketiminato ligand, which shows transition-metal-like reactivity with dialkylamine–boranes H₃B·NHR₂ (R = CH₃, Cy, C₆H₅CH₂, and ⁱPr) to afford unprecedented amine–borane coordinated complexes through Ca⋯H interactions. This calcium aryloxide was also an active catalyst in dehydrogenation of amine–boranes, and gave aminoboranes H₂BNR₂, as the sole product. The initiating species was a calcium amine–borane complex rather than the traditional calcium amidoborane complex formed by σ-bond metathesis.

链接：https://pubs.rsc.org/en/content/articlelanding/2019/CC/C9CC04698D#!divAbstract