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<p>The reaction of tin tetrachloride with a series of fluorinated phosphoramidates bearing alkylamino groups of the type (R<sub>F</sub>O)<sub>2</sub>P(O)NHR (L) in anhydrous dichloromethane produces new octahedral tin complexes of the general formula [SnCl<sub>4</sub>L<sub>2</sub>]. These adducts were characterized by multinuclear (<sup>1</sup>H, <sup>13</sup>C, <sup>31</sup>P and <sup>119</sup>Sn) NMR, IR spectroscopy, and elemental analysis. The NMR data show that these complexes exist in solution at room temperature as mixtures of <i>cis</i> and <i>trans</i> isomers with predominance of the <i>cis</i> form. In addition, the solution behavior of these complexes in the presence of excess ligand was studied with variable temperature NMR. The metal-ligand exchange barriers of the <i>cis</i> isomers were measured using the coalescence temperature method, giving values in the range 11.70-12.58&#xa0;kcal/mol. The predominance of the <i>cis</i> isomer was interpreted in terms of a weaker donor ability of these alkyl amino containing phosphoramidate ligands as compared to analogous dialkylamino based derivatives, (R<sub>F</sub>O)<sub>2</sub>P(O)NR<sub>2</sub>. This is consistent with a higher frequency shift (⁓10 ppm) of <sup>119</sup>Sn NMR signals for tin complexes with the former ligands than with that of the latter phosphoramidates, suggesting that the substitution of a dialkylamino by an alkylamino group does reduce the donor ability of such ligands. The results were also based on comparison with those previously described for closely related SnCl<sub>4</sub> adducts.</p>

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Synthesis, Spectroscopic Characterization and Solution Behavior of tin(IV) Chloride Complexes with Highly Fluorinated Phosphoramidates

  • 期刊论文

  • 发表日期：

    2026年3月4日

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  • Samar Argoubi,
  • Med Abderrahmane Sanhoury,
  • Eric Manoury,
  • Ikram Chehidi

摘要

The reaction of tin tetrachloride with a series of fluorinated phosphoramidates bearing alkylamino groups of the type (RFO)2P(O)NHR (L) in anhydrous dichloromethane produces new octahedral tin complexes of the general formula [SnCl4L2]. These adducts were characterized by multinuclear (1H, 13C, 31P and 119Sn) NMR, IR spectroscopy, and elemental analysis. The NMR data show that these complexes exist in solution at room temperature as mixtures of cis and trans isomers with predominance of the cis form. In addition, the solution behavior of these complexes in the presence of excess ligand was studied with variable temperature NMR. The metal-ligand exchange barriers of the cis isomers were measured using the coalescence temperature method, giving values in the range 11.70-12.58 kcal/mol. The predominance of the cis isomer was interpreted in terms of a weaker donor ability of these alkyl amino containing phosphoramidate ligands as compared to analogous dialkylamino based derivatives, (RFO)2P(O)NR2. This is consistent with a higher frequency shift (⁓10 ppm) of 119Sn NMR signals for tin complexes with the former ligands than with that of the latter phosphoramidates, suggesting that the substitution of a dialkylamino by an alkylamino group does reduce the donor ability of such ligands. The results were also based on comparison with those previously described for closely related SnCl4 adducts.