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首页> 外文期刊>Journal of Organometallic Chemistry >Reduction of C,O-chelated organotin(IV) dichlorides and dihydrides leading to protected polystannanes
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Reduction of C,O-chelated organotin(IV) dichlorides and dihydrides leading to protected polystannanes

机译：还原C，O螯合的有机锡（IV）二氯化物和二氢化物，导致保护的聚锡酮

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A series of aryloxy organotin compounds Ph3Sn(CH2)(3)OC6H4R (5: R = H; 6: R = Ph; 7: R = OCH3, 8: R = CF3), Ph2ClSn(CH2)(3)OC6H4R (9: R = H; 10: R = Ph) and PhCl2Sn(CH2)(3)OC6H4R (12: R = H; 13: R = Ph) have been synthesized and characterised by NMR (H-1, C-13, Sn-119) spectroscopy. X-ray structure determinations of 9, 10, 12 and 13 reveal a distorted trigonal bipyramidal geometry at Sn with Cl trans to the datively bonded O whereas 8 possesses tetrahedral geometry and a Sn center dot center dot center dot O dative interaction is absent. Triorganotin hydrides Ph2HSn(CH2)(3)OC6H4R (14: R = H; 15: R = Ph) and diorganotin dihydrides PhH2Sn(CH2)(3)OC6H4R (16: R = H; 17: R = Ph) were prepared by reduction of the corresponding dihalides with LiAlH4. Catalytic dehydrocoupling of dihydrides 16 or 17 with a late transition metal catalyst afforded asymmetrical hypercoordinated polystannanes [PhSn(CH2)(3)OC6H4R](n) (18: R = H; 19: R = Ph) with relatively high molecular weights (M-w = 1.3 x 10(4) - 2.5 x 10(5) Da) and narrow polydispersities (PDI's = 1.3-3.3). NMR and UV-Vis spectroscopy studies indicate that the new polymers display dramatically improved light stability, but remain sensitive to moisture. (C) 2014 Elsevier B.V. All rights reserved.
机译：一系列芳氧基有机锡化合物Ph3Sn（CH2）（3）OC6H4R（5：R = H; 6：R = Ph; 7：R = OCH3，8：R = CF3），Ph2ClSn（CH2）（3）OC6H4R（9 ：R ＝ H; 10：R ＝ Ph）和PhCl 2 Sn（CH 2）（3）OC 6 H 4 R（12：R ＝ H; 13：R ＝ Ph）已经合成并通过NMR（H-1，C-13，Sn）表征。 -119）光谱。 X射线结构测定9、10、12和13揭示了Sn处扭曲的三角双锥几何结构，Cl传递到键合的O上，而8位具有四面体几何结构，并且没有Sn中心点中心点中心点O固有的相互作用。制备三有机锡氢化物Ph2HSn（CH2）（3）OC6H4R（14：R = H; 15：R = Ph）和二有机锡二氢化物PhH2Sn（CH2）（3）OC6H4R（16：R = H; 17：R = Ph）用LiAlH4还原相应的二卤化物。二氢化物16或17与后期过渡金属催化剂的催化脱氢偶联反应提供了相对较高的分子量（Mw）不对称的高配位聚锡烷[PhSn（CH2）（3）OC6H4R]（n）（18：R = H; 19：R = Ph） = 1.3 x 10（4）-2.5 x 10（5）Da）和窄多分散性（PDI's = 1.3-3.3）。 NMR和UV-Vis光谱研究表明，新聚合物显示出显着改善的光稳定性，但仍对水分敏感。 （C）2014 Elsevier B.V.保留所有权利。

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