β-丁氧酯基三氯化锡与席夫碱配合物的合成、结构与酯交换反应

Synthesis, Crystal Structure, Transesterifications of the Complex of β - Butoxycarbonylethyltin Trichlorides with Schiff Base Ligands

合成了标题化合物n-BuO_2CCH_2CH_2SnCl_3·(2-HOC_6H_4CH=NC_6H_4-OMe-4’),通过元素分析,UV-Vis,IR和~1H NMR进行了表征。其晶体结构分析表明,该晶体属单斜晶系,空间群P2_1/c;a=1.4661(3),b=0.9307(2),c=1.7888(4)nm,β=94.04(3)°,Mr=579.45,Z=4;V=2.4348(8)nm^3,Dc=1.581mg/m^3,μ=1.405mm^(-1),F(000)=1160,R=0.0354,Rw=0.0486。该化合物为含有分子内羰基氧配位,Schiff碱以酚羟基上的氧原子配位,中心锡原子为六配位,空间构型为畸变八面体构型的单分子有机锡化合物。研究了标题化合物在醇中的酯交换反应,合成了8个配合物RO_2CCH_2CH_2SnCl_3·(2-HOC_6H_4CH=NC_6H_4OMe-4’)(其中R=Me,Et,n-Pr,i-Pr,n-Am,i-Am,Cl-C_2H_4-,(CH_3CH_2)_2CHCH_2-),并对它们进行了表征,提出了酯交换反应的机理。

Title complex n - BuO2CCH2CH2SnCl3 · (2 - HOC6H4CH = NC6H4OMe - 4') was synthesized and characterized by elemental analysis, UV - Vis, IR, 1H NMR. The crystal structure was determined by the X - ray diffraction analysis.The crystal belong to monoclinic system, space group P21/c with a = 1.4661(3), b - 0.9307(2), c = 1.7888 (4) nm, β = 94.04(3);Z = 4. The complex exists as a discrete molecule, and the in atom attains a distorted octahedral geometry vis the coordination of intramolecular carbonyl oxygen and phenolic oxygen of the Schiff base. The coordination number of tin atom is 6. The transesterification of title complex with ROH was studied and 8 new complexes RO2CCH2CH2SnCl3 · (2 -HOC6H4CH = NC6H4OMe-4') (R = Me, Et, Pr, i-Bu, n - Am, i - Am, Cl-C2H4, (CH3CH2)2CHCH2 - ) were obtained. The possible mechanism is suggested.