Formation mechanisms, structure, solution behavior, and reactivity of aminodiborane

Journal of the American Chemical Society
Huizhen LiXuenian Chen

Abstract

A facile synthesis of cyclic aminodiborane (NH2B2H5, ADB) from ammonia borane (NH3·BH3, AB) and THF·BH3 has made it possible to determine its important characteristics. Ammonia diborane (NH3BH2(μ-H)BH3, AaDB) and aminoborane (NH2BH2, AoB) were identified as key intermediates in the formation of ADB. Elimination of molecular hydrogen occurred from an ion pair, [H2B(NH3) (THF)](+)[BH4](-). Protic-hydridic hydrogen scrambling was proved on the basis of analysis of the molecular hydrogen products, ADB and other reagents through (2)H NMR and MS, and it was proposed that the scrambling occurred as the ion pair reversibly formed a BH5-like intermediate, [(THF)BH2NH2](η(2)-H2)BH3. Loss of molecular hydrogen from the ion pair led to the formation of AoB, most of which was trapped by BH3 to form ADB with a small amount oligomerizing to (NH2BH2)n. Theoretical calculations showed the thermodynamic feasibility of the proposed intermediates and the activation processes. The structure of the ADB·THF complex was found from X-ray single crystal analysis to be a three-dimensional array of zigzag chains of ADB and THF, maintained by hydrogen and dihydrogen bonding. Room temperature exchange of terminal and bridge hydrogens in ADB was observed in ...Continue Reading

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Citations

Sep 15, 2016·Angewandte Chemie·Étienne RochetteFrédéric-Georges Fontaine
Mar 28, 2016·Chemistry : a European Journal·Weidong ChenPing Chen
Mar 28, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xin-Ran LiuXuenian Chen
Mar 14, 2019·Chemistry : a European Journal·Estefanía Del HornoCarlos Yélamos
Apr 10, 2019·Chemistry : a European Journal·Devin H A BoomJ Chris Slootweg
Oct 9, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xi-Meng ChenXuenian Chen
Nov 17, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Huizhen LiYanfeng Yue
Jan 26, 2021·Chemical Communications : Chem Comm·Binayak RoyPratibha Sharma
Nov 13, 2021·Chemical Communications : Chem Comm·Xinying LiXuenian Chen

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