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<p>The chemistry of phosphaalumenes [R–Al=P–R’] featuring multiple bonds between phosphorus and aluminum remains largely unexplored. Here we show the syntheses of a phosphaalumene(3) through either the reaction of <sup>Dipp</sup>NacNacM (<sup>Dipp</sup>NacNac = HC[(CMe)N(2,6-<sup><i>i</i></sup>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)]<sub>2</sub>, M = Al) with a bisphosphirane-fused anthracene (<b>1</b>) or with a phospha-Wittig reagent (<b>2</b>) under mild conditions. This phosphaalumene exhibits reactivities that stand in contrast to those of previously reported transient species <b>II</b>, especially in its ability to activate small molecules such as dihydrogen (H<sub>2</sub>), white phosphorus (P<sub>4</sub>), isocyanides, CO<sub>2</sub>, N<sub>2</sub>O, trimethylsilyl azide (TMSN<sub>3</sub>), diphenyl diselenide (PhSeSePh), PhSiH<sub>3</sub>, PhNH<sub>2</sub>, styrene and 1-ethynyl-4-methylbenzene. It has been found in this research that the ligand environment can have a subtle but profound impact on the reactivity of phosphaalumenes.</p>

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An isolable phosphaalumene(3) capable of small molecule activation via unique modes of reactivity

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月5日

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  • Yan Cha,
  • Zhaoziyuan Yang,
  • Xiao Zhuang,
  • Pengyu Gao,
  • Tingting Liu,
  • Fei Luo,
  • Xianjia Ni,
  • Qing Luo,
  • Wei Lu

摘要

The chemistry of phosphaalumenes [R–Al=P–R’] featuring multiple bonds between phosphorus and aluminum remains largely unexplored. Here we show the syntheses of a phosphaalumene(3) through either the reaction of DippNacNacM (DippNacNac = HC[(CMe)N(2,6-iPr2C6H3)]2, M = Al) with a bisphosphirane-fused anthracene (1) or with a phospha-Wittig reagent (2) under mild conditions. This phosphaalumene exhibits reactivities that stand in contrast to those of previously reported transient species II, especially in its ability to activate small molecules such as dihydrogen (H2), white phosphorus (P4), isocyanides, CO2, N2O, trimethylsilyl azide (TMSN3), diphenyl diselenide (PhSeSePh), PhSiH3, PhNH2, styrene and 1-ethynyl-4-methylbenzene. It has been found in this research that the ligand environment can have a subtle but profound impact on the reactivity of phosphaalumenes.