Spirocyclic tin salicyl alcoholates - a combined experimental and theoretical study on their structures, 119Sn NMR chemical shifts and reactivity in thermally induced twin polymerization.
Spirocyclic tin salicyl alcoholates - a combined experimental and theoretical study on their structures, 119Sn NMR chemical shifts and reactivity in thermally induced twin polymerization.
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DOI：
10.1039/c8dt03695k
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发表时间：
2019-01
影响因子：
4
通讯作者：
Philipp Kitschke;A. Preda;A. Auer;S. Scholz;T. Rüffer;H. Lang;M. Mehring
中科院分区：
文献类型：
--
作者：
Philipp Kitschke;A. Preda;A. Auer;S. Scholz;T. Rüffer;H. Lang;M. Mehring
合成了螺环水杨醇锡化合物4 H，4 'H-2，2'-螺环[苯并[d][1，3，2]二氧杂锡]（1）及其6，6 '-二甲氧基（2）和8，8'-二叔丁基-6，6 '-二甲基衍生物（3），并将其前驱体2进行热诱导孪晶聚合，得到含SnO 2杂化材料。用~（119）Sn {~ 1H} CP MAS NMR谱和密度泛函理论计算研究了1-3的分子结构。化合物3从二甲基亚砜溶液中结晶得到固体状态下具有六配位锡原子的刘易斯酸碱加合物3（dmso）2，与光谱和DFT计算数据的结果一致。化合物1-3和3（dmso）2的119 Sn NMR光谱揭示了溶液相中指向六配位锡原子的不同低聚物之间的平衡。
The spirocyclic tin salicyl alcoholate, 4H,4'H-2,2'-spirobi[benzo[d][1,3,2]dioxastannine] (1), and its 6,6'-dimethoxy (2) and 8,8'-di-tert-butyl-6,6'-dimethyl derivative (3) were synthesized and thermally induced twin polymerization of precursor 2 was performed to give a SnO2-containing hybrid material. Studies on the molecular structures of 1-3 were carried out using 119Sn{1H} CP MAS NMR spectroscopy and DFT calculations. Crystallization of compound 3 from dimethyl sulfoxide solution provided the Lewis acid-base adduct 3(dmso)2 exhibiting a hexacoordinated tin atom in the solid state, in agreement with the results of the spectroscopic and DFT calculation data. 119Sn NMR spectroscopy of the compounds 1-3 and 3(dmso)2 revealed equilibria among the diverse oligomers in solution phase pointing at hexacoordinated tin atoms.