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<p>New tetrylenes were synthesized by the reaction of amino bisphenols (2-HO-3-R<sup>1</sup>-5-MeC<sub>6</sub>H<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>NR<sup>2</sup> (R<sup>1</sup> = Bu<sup>t</sup>, CMe<sub>2</sub>Ph; R<sup>2</sup> = Bu, Bn) with the Lappert’s tetrylenes M[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub> (M = Ge, Sn). The structures of the synthesized complexes were confirmed by <sup>1</sup>H, <sup>13</sup>C, and <sup>119</sup>Sn NMR spectroscopy and high-resolution mass spectrometry. The structure of the monomeric germylene with R<sup>1</sup> = CMe<sub>2</sub>Ph and R<sup>2</sup> = Bu was determined by X-ray diffraction. The frontier molecular orbitals of a number of complexed germylenes were analyzed in comparison to the uncomplexed analog (PBE0/L1). The additional coordination bond was found to affect the reactivity of germylenes in oxidative addition reactions. These data correlate with the relative chemical inertness of tetrylenes in the insertion reaction with iodomethane.</p>

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Germylenes and stannylenes based on amino bisphenols: synthesis, molecular and electronic structure

  • 期刊论文

  • 发表日期：

    2026年2月1日

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  • S. V. Timofeev,
  • E. A. Zakharova,
  • M. V. Zabalov,
  • B. N. Mankaev,
  • M. A. Syroeshkin,
  • K. A. Lyssenko,
  • M. P. Egorov,
  • S. S. Karlov

摘要

New tetrylenes were synthesized by the reaction of amino bisphenols (2-HO-3-R1-5-MeC6H2CH2)2NR2 (R1 = But, CMe2Ph; R2 = Bu, Bn) with the Lappert’s tetrylenes M[N(SiMe3)2]2 (M = Ge, Sn). The structures of the synthesized complexes were confirmed by 1H, 13C, and 119Sn NMR spectroscopy and high-resolution mass spectrometry. The structure of the monomeric germylene with R1 = CMe2Ph and R2 = Bu was determined by X-ray diffraction. The frontier molecular orbitals of a number of complexed germylenes were analyzed in comparison to the uncomplexed analog (PBE0/L1). The additional coordination bond was found to affect the reactivity of germylenes in oxidative addition reactions. These data correlate with the relative chemical inertness of tetrylenes in the insertion reaction with iodomethane.