Activation of Triphenylphosphine Oxide Mediated by Trivalent Organouranium Species
Activation of Triphenylphosphine Oxide Mediated by Trivalent Organouranium Species
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三价有机铀介导的三苯基氧化膦的活化
DOI：
10.1021/acs.organomet.7b00896
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发表时间：
2018
期刊：
影响因子：
2.8
通讯作者：
Bart, Suzanne C.
中科院分区：
文献类型：
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作者：
Tatebe, Caleb J.;Tong, Zhengjia;Kiernicki, John J.;Coughlin, Ezra J.;Zeller, Matthias;Bart, Suzanne C.
由两个氢（3,5-二甲基吡唑基）硼酸盐（Tp*）配体支撑的一类铀苄基化合物，Tp*2U(CH2Ph) (1-Bn), Tp*2U(ch2 -对- iprph) (1-iPr), Tp*2U(ch2 -对- tbuph) （1-tBu）或Tp*2U(ch2 -间- omeph) (1-OMe)，与单一的三苯基氧化膦（OPPh3）等价物处理，导致独特的碳-碳偶联发生。该反应的产物Tp*2U[OP(C6H5)2(C6H5CH2C6H5)] （2- ph）、Tp*2U[OP(C6H5)2(C6H5CH2-p-iPrC6H4)] （2- ipr）、Tp*2U[OP(C6H5)2(C6H5CH2-p-tBuC6H4)] （2- tbu）和Tp*2U[OP(C6H5)2(C6H5CH2-m-OCH3C6H4)] （2- ome）通过苯基取代基与OPPh3的一个苯基对碳之间的偶联表征。为了探索这种不寻常的反应性，用不同的三（芳基）膦氧化物处理1- bn1，包括三（对甲基）膦氧化物，生成Tp*2U[OP（对甲基）2(C6H4(CH3)CH2C6H5)]（3-甲基）。所有化合物都通过多核核磁共振、振动和电子吸收光谱进行了表征。在可能的情况下，使用x射线衍射来确认分子结构。
Treating a family of uranium benzyl compounds, Tp*2U(CH2Ph) (1-Bn), Tp*2U(CH2-para-iPrPh) (1-iPr), Tp*2U(CH2-para-tBuPh) (1-tBu), or Tp*2U(CH2-meta-OMePh) (1-OMe), which are supported by two hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligands, with a single equivalent of triphenylphosphine oxide (OPPh3) causes a unique carbon–carbon coupling to occur. The products of this reaction, Tp*2U[OP(C6H5)2(C6H5CH2C6H5)] (2-Ph), Tp*2U[OP(C6H5)2(C6H5CH2-p-iPrC6H4)] (2-iPr), Tp*2U[OP(C6H5)2(C6H5CH2-p-tBuC6H4)] (2-tBu), and Tp*2U[OP(C6H5)2(C6H5CH2-m-OCH3C6H4)] (2-OMe), are characterized by coupling between the benzyl substituent and thepara-carbon of one of the phenyl groups of OPPh3. To probe the scope of this unusual reactivity,1-Bnwas treated with different tris(aryl)phosphine oxides, including tris(p-tolyl)phosphine oxide, which yields Tp*2U[OP(p-tolyl)2(C6H4(CH3)CH2C6H5)] (3-tolyl). All compounds were characterized by multinuclear NMR, vibrational, and electronic absorption spectroscopies. When possible, X-ray diffraction was used to confirm molecular structures.