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氟化三芳基铝配合物的合成与反应活性

Synthesis and Reactivity of Fluorinated Triaryl Aluminum Complexes.

作者信息

Ould Darren M C, Carden Jamie L, Page Rowan, Melen Rebecca L

机构信息

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Cardiff CF10 3AT, Cymru/Wales, U.K.

出版信息

Inorg Chem. 2020 Oct 19;59(20):14891-14898. doi: 10.1021/acs.inorgchem.0c01076. Epub 2020 Sep 1.

Abstract

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.

摘要

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。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/adae/7581293/42753c87b461/ic0c01076_0001.jpg

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