Difluorination at Boron Leads to the First Electrophilic Ligated Boryl Radical (NHC‐BF2.),Angewandte Chemie International Edition

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Difluorination at Boron Leads to the First Electrophilic Ligated Boryl Radical (NHC‐BF2.)
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-17 , DOI: 10.1002/anie.201806476
Daniel Subervie ₁ , Bernadette Graff ₂ , Swapnil Nerkar ₃ , Dennis P. Curran ₃ , Jacques Lalevée ₂ , Emmanuel Lacôte ₁

Affiliation

1,3‐Dimethylimidazol‐2‐ylidene difluoroborane (NHC‐BF₂H) was prepared in a one‐pot, two‐step reaction from the parent ligated borane (NHC‐BH₃). The derived difluoroboryl radical (NHC‐BF₂^.) was generated by laser flash photolysis experiments and characterized by UV spectroscopy and rate‐constant measurements. It is transient and reacts quickly with O₂. Unusually, it also reacts more rapidly with ethyl vinyl ether than with methyl acrylate. By this measure, it is the first electrophilic ligated boryl radical. Both NHC‐BH₃ and NHC‐BF₂H serve as co‐initiators in bulk photopolymerizations, converting both electron‐poor and electron‐rich monomers at roughly similar rates. However, the difluorinated coinitiator provides polymers with dramatically increased chain lengths from both monomers.

中文翻译：

硼的二氟化导致第一个亲电的硼烷基自由基（NHC-BF2。）

1,3-二甲基咪唑-2-亚甲基二氟硼烷（NHC- BF ₂ H）是从母体连接的硼烷（NHC-BH ₃）通过一锅，两步反应制备的。派生difluoroboryl自由基（NHC-BF ₂^。）用激光闪光光解实验中产生和表征通过UV光谱和速率常数的测量。它是瞬态的，并与O ₂迅速反应。通常，它与乙基乙烯基醚的反应也比与丙烯酸甲酯的反应更快。通过这种方法，它是第一个亲电连接的硼基。NHC-BH ₃和NHC-BF ₂H用作本体光聚合中的共引发剂，以大致相似的速率转化贫电子单体和富电子单体。然而，二氟化共引发剂使两种单体的聚合物链长大大增加。

更新日期：2018-07-17

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