Liu Han-Ying, Mahon Mary F, Hill Michael S
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Inorg Chem. 2023 Sep 18;62(37):15310-15319. doi: 10.1021/acs.inorgchem.3c02566. Epub 2023 Sep 6.
The potassium diamidoalumanyl, [K{Al(SiN)}] (SiN = {CHSiMeNDipp}), reacts with the terminal B-O bonds of pinacolato boron esters, ROBpin (R = Me, -Pr), and B(OMe) to provide potsassium (alkoxy)borylaluminate derivatives, [K{Al(SiN)(OR)(Bpin)}] (R = Me, = 2; R = -Pr, = ∞) and [K{Al(SiN)(OMe)(B(OMe))}], comprising Al-B σ bonds. An initial assay of the reactivity of these species with the heteroallene molecules, ,'-diisopropylcarbodiimide and CO, highlights the kinetic inaccessibility of their Al-B bonds; only decomposition at high temperature is observed with the carbodiimide, whereas CO preferentially inserts into the Al-O bond of [K{Al(SiN)(OMe)(Bpin)}] to provide a dimeric methyl carbonate species. Treatment of the acyclic dimethoxyboryl species, however, successfully liberates a terminal alumaboronic ester featuring trigonal NAl-BO coordination environments at both boron and aluminum.
二氨基铝钾[K{Al(SiN)}]（SiN = {CHSiMeNDipp}）与频哪醇硼酸酯ROBpin（R = Me，-Pr）和B(OMe)的末端B - O键反应，生成含Al - B σ键的钾（烷氧基）硼铝酸盐衍生物[K{Al(SiN)(OR)(Bpin)}]（R = Me，= 2；R = -Pr，= ∞）和[K{Al(SiN)(OMe)(B(OMe))}]。对这些物种与杂丙二烯分子、,'-二异丙基碳二亚胺和CO反应活性的初步测定表明，它们的Al - B键在动力学上难以接近；与碳二亚胺反应时，仅在高温下观察到分解，而CO优先插入[K{Al(SiN)(OMe)(Bpin)}]的Al - O键中，生成二聚碳酸甲酯物种。然而，对无环二甲氧基硼基物种的处理成功地释放出一种末端铝硼酸酯，其在硼和铝处均具有三角NAl - BO配位环境。
