Activation of Triphenylphosphine Oxide Mediated by Trivalent Organouranium Species

作者：Tatebe Caleb J; Tong Zhengjia; Kiernicki John J; Coughlin Ezra J; Zeller Matthias; Bart Suzanne C^*

来源：Organometallics, 2018, 37(6): 934-940.

DOI：10.1021/acs.organomet.7b00896

Treating a family of uranium benzyl compounds, Tp*U-2(CH2Ph) (1-Bn), Tp*U-2(CH2-para-(PrPh)-Pr-i) (1-Pr-i), TP*(2)-U(CH2-para-BuPh) (1-Bu-t), or Tp*U-2(CH(2)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*U-2[OP(C6H5)(2)(C(6)HsCH(2)C(6)Hs)] (2-Ph), Tp*U-2[OP-(C6H5)(2)-(C6H5CH2-p-iPrC(6)H(4))] (2-Pr-i), Tp*U-2[OP(C6H5)(2)-(C6H5CH2-p-tBuC(6)H(4))] (2-Bu-t), and Tp*U-2[OP(C6H5)(2)(C6H5-CH2-m-OCH3C6H4)] (2-OMe), are characterized by coupling between the benzyl substituent and the para-carbon of one of the phenyl groups of OPPh3. To probe the scope of this unusual reactivity, 1-Bn was treated with different tris(aryl)phosphine oxides, including tris(p-tolyl)phosphine oxide, which yields Tp*U-2[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.

• 出版日期2018-3-26