期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 13, 页码 5099-5105出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c00779
关键词
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资金
- National Science Foundation of China [22031003, 21720102004]
- Shanghai Science Technology Committee [19DZ2270100]
This study demonstrates how steric effects can be used to achieve regioselective B-H activation in para-carboranes, with different activation patterns achieved by utilizing pi-pi interactions between pyridine ligands and host-guest interactions in metallacage compounds.
The controllable B-H bond activation of carboranes has long been a compelling challenge. However, as the symmetry of para-carborane places the same charge on all of its ten boron atoms, controlling the regiochemistry of B-H bond activation in these molecules has remained out of reach ever since their discovery. Herein, we describe how to use steric effects to achieve a regioselective process for B-H activation of para-carborane. In this strategy, B(2,8)-H or B(2,7)-H activation patterns were achieved by taking advantage of the pi-pi interactions between pyridine ligands. Interestingly, by employing host-guest interactions in metallacage compounds, B(2,8)-H bond activation could be avoided and exclusive B(2,9)-H bond activation can be achieved. Steric hindrance was also found to be beneficial for regioselective B(2,8)-H bond activation in metallacage species. In this work, we demonstrate that steric effects can be a promising driving force for controllable activation of the B-H bonds of carboranes and open new opportunities in this field.
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