立体拥挤的锡酰膦和锡胺的多核磁共振研究:对化学屏蔽和自旋-自旋耦合的立体化学影响

Armin Dörr, D. Gudat, Dieter Hänssgen, H. Hens, E. Stahlhut
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摘要

空间拥挤无环苯基膦的多核(1H, 15N, 29Si, 31P, 119Sn)核磁共振数据1- 3,10), (tBu2RSn)2PH (R = Me, Cl;4,5), tBu3SnPY2 (Y = SnMe3, SiMe3;6,11), PH(SntBu2PHSntBu3)2 (7), SntBu2(PY2)2 (Y = H, SiMe3, PHSntBu3;8, 9, 12),环苯基膦(tBu2SnPY)n (n = 2, Y = H, C3H6Cl, tBu, SnMe3;13 - 16;n = 3, Y = H;18), (Me2SnPSntBu3)2(17),和锡胺tBu3SnNHY (Y = H, SnMe3, SntBu3;通过各种1D和2d技术获得了19-21)。31P-和15n -屏蔽可以定性地解释为两个相互抵消的影响,即电负性差异和取代基的空间要求。类似地,单键耦合1KSnP和1KSnM的趋势可以用一个简单的模型来合理化,该模型基于立体要求取代基对键角的变形。可以确定2KSnPH和1KPSnCCH的远程耦合信号,这可能对未来的结构研究有用。光谱13和18中的温度依赖效应可以得出分子构象动力学的结论。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Multinuclear magnetic resonance study of sterically crowded stannylphosphines and stannylamines : stereochemical influences on chemical shielding and spin-spin couplings
Multinuclear (1H, 15N, 29Si, 31P, 119Sn) NMR data of sterically crowded acyclic stannylphosphines tBu3SnPHY (Y = H, SnMe3, SntBu3, SiMe3; 1-3, 10), (tBu2RSn)2PH (R = Me, Cl; 4, 5), tBu3SnPY2 (Y = SnMe3, SiMe3; 6, 11), PH(SntBu2PHSntBu3)2 (7), SntBu2(PY2)2 (Y = H, SiMe3, PHSntBu3; 8, 9, 12), cyclic stannylphosphines (tBu2SnPY)n (n = 2, Y = H, C3H6Cl, tBu, SnMe3; 13-16; n = 3, Y = H; 18), (Me2SnPSntBu3)2 (17), and stannylamines tBu3SnNHY (Y = H, SnMe3, SntBu3; 19-21) were obtained by various 1D- and 2D-techniques. 31P- and 15N-shieldings may be explained qualitatively in terms of two counteracting influences, viz electronegativity differences and steric requirements of the substituents. In a similar manner, the trends in one-bond coupling 1KSnP and 1KSnM may be rationalized using a simple model based on the deformation of bond angles by sterically demanding substituents. The signs of long-range couplings 2KSnPH and 1KPSnCCH could be determined, which may be useful for future structural studies. Temperature-dependent effects in the spectra of 13, 18 allow conclusions about the conformational dynamics of the molecules.
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