Ould Darren M C, Carden Jamie L, Page Rowan, Melen Rebecca L
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Cardiff CF10 3AT, Cymru/Wales, U.K.
Inorg Chem. 2020 Oct 19;59(20):14891-14898. doi: 10.1021/acs.inorgchem.0c01076. Epub 2020 Sep 1.
The addition of the Grignard 3,4,5-ArMgBr to aluminum(III) chloride in ether generates the novel triarylalane Al(3,4,5-Ar)·OEt. Attempts to synthesize this alane via transmetalation from the parent borane with trimethylaluminum gave a dimeric structure with bridging methyl groups, a product of partial transmetalation. On the other hand, the novel alane Al(2,3,4-Ar) was synthesized from the parent borane and trimethylaluminum. Interestingly, the solid-state structure of Al(2,3,4-Ar) shows an extended chain structure resulting from neighboring Al···F contacts. Al(3,4,5-Ar)·OEt was then found to be an effective catalyst for the hydroboration of carbonyls, imines, and alkynes with pinacolborane.
在乙醚中，将格氏试剂3,4,5 - ArMgBr加入到氯化铝(III)中，生成了新型三芳基铝烷Al(3,4,5 - Ar)·OEt。尝试通过母体硼烷与三甲基铝进行金属转移反应来合成这种铝烷，得到了一种具有桥连甲基的二聚体结构，这是部分金属转移反应的产物。另一方面，新型铝烷Al(2,3,4 - Ar)是由母体硼烷和三甲基铝合成的。有趣的是，Al(2,3,4 - Ar)的固态结构显示出由相邻的Al···F接触导致的延伸链结构。然后发现Al(3,4,5 - Ar)·OEt是用频哪醇硼烷对羰基、亚胺和炔烃进行硼氢化反应的有效催化剂。
