4.5 Article

B-Centered Reactivity of Persistent P-Stabilized Boryl Radicals

期刊

ORGANOMETALLICS
卷 37, 期 5, 页码 755-760

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.7b00598

关键词

-

资金

  1. Centre National de la Recherche Scientifique (CNRS)
  2. Universite Paul Sabatier (UPS)
  3. CDAPP

向作者/读者索取更多资源

A new P-stabilized boryl radical [iPr(2)P(naph)BMes](center dot) 2a was obtained by reduction of the corresponding phosphino-bromoborane la with Na(Hg). The persistent radical 2a has been characterized by EPR, and its structure has been thoroughly studied by DFT. The corresponding Gomberg-type dimer has been analyzed by NMR and XRD, and the Gibbs free energy associated with the dimerization process has been evaluated by VT EPR. The replacement of the Ph substituents at phosphorus for iPr groups has a slight but noticeable impact: it increases the spin density at boron and favors the radical over its Gomberg-type dimer. An original cross-coupling product between 2a and the trityl radical Ph3C(center dot) has also been authenticated crystallographically. The P-stabilized boryl radicals 2a,b are readily trapped by TEMPO to give the corresponding B-O adducts 3a,b (naphthyl-bridged phosphine-boranes without P -> B interaction). The reaction of 2a,b with Ph3CCl substantiates their ability to participate in halogen transfer reactions.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.5
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据