<sup>1</sup>H NMR Studies on the Interactions of Acyclic Polyethers with Dimethyltin Bichloride in Aromatic Solvents
作者:Junzo Otera、Tadashi Shiomi、Kazuhiko Murakami、Yoshikane Kawasaki
DOI:10.1246/bcsj.54.2964
日期:1981.10
The interactions between various acyclic polyethers, RO(CH2CH2O)nR′(R, R′=CH3, Ph), and dimethyltin dichloride (DMTC) in aromatic solvents have been studied by means of 1H NMR spectroscopy. On the basis of a continuous variation method, the formation of the 1 : 1 complexes between glymes, CH3O(CH2CH2O)nCH3(n=2, 3, 4), and DMTC was revealed in benzene. The 2J(119Sn–CH3) values suggested distorted trans-octahedral configurations for these complexes. From the statistical consideration of stability constants, it was found that the coordination occurred virtually through neighboring two oxygen atoms in these complexes. DMTC gave the complexes of both 1 : 1 and 1 : 2 glyme/DMTC stoichiometry with glymes (n=5, 6) in benzene and with all glymes employed here in toluene and 1-chloronaphthalene. Coexistence of 1 : 1 and 1 : 2 species was also encountered for PhO(CH2CH2O)nCH3 (n=3, 4, 5), whereas no appreciable interaction was observed between PhO(CH2CH2O)nPh (n=2, 3, 4) and DMTC. On the basis of these observations, the additional formation of the 1 : 2 complexes was assumed to be caused by the bulkiness of polyethers.
通过 1H NMR 光谱法研究了各种无环聚醚、RO(CH2CH2O)nR′(R, R′=CH3, Ph)和二甲基二氯化锡(DMTC)在芳香溶剂中的相互作用。根据连续变化的方法,揭示了在苯中乙二胺、CH3O(CH2CH2O)nCH3(n=2、3、4)和 DMTC 之间形成的 1 : 1 复合物。2J(119Sn-CH3) 值表明这些配合物具有扭曲的反八面体构型。从稳定性常数的统计考虑发现,这些配合物中的配位实际上是通过相邻的两个氧原子进行的。在苯中,DMTC 与乙二胺(n=5、6)以及在甲苯和 1-氯萘中与此处使用的所有乙二胺配位,生成了 1 : 1 和 1 : 2 乙二胺/DMTC 配比的络合物。在 PhO(CH2CH2O)nCH3(n=3、4、5)中也出现了 1 : 1 和 1 : 2 的共存现象,而在 PhO(CH2CH2O)nPh(n=2、3、4)和 DMTC 之间没有观察到明显的相互作用。根据这些观察结果,我们推测 1 : 2 复合物的额外形成是由聚醚的体积造成的。