Zhang Yongliang, Wei Junnian, Zhang Wen-Xiong, Xi Zhenfeng
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences , Shanghai 200032, China.
Inorg Chem. 2015 Nov 16;54(22):10695-700. doi: 10.1021/acs.inorgchem.5b01551. Epub 2015 Oct 26.
A series of lithium aluminate complexes and alumoles were synthesized from 1,4-dilithio-1,3-butadienes 1 and AlEt2Cl. Their structures were characterized using single-crystal X-ray structural analysis and NMR spectroscopy. The structure of the lithium aluminate complex 2-TMEDA showed that the Al atom adopted a tetra-coordinated mode bonded with two butadienyl Csp2 atoms and two ethyl Csp3 atoms. The lithium cation was located above the alumole ring. The structure of 3a revealed a dimeric 1-ethylalumole in the solid state. Diffusion ordered spectroscopy NMR spectra showed that 3a was also a dimer in C6D6 solvent. However, in tetrahydrofuran (THF) solution, the dimeric 3a dissociated into the 1-ethylalumole-THF adduct. The lithium aluminate complex 2 transformed into 3a-THF when treated with 1.0 equiv of AlEt2Cl. Preliminary reaction chemistry and synthetic applications of the lithium aluminate complex were also investigated.
由1,4-二锂-1,3-丁二烯1和AlEt2Cl合成了一系列铝酸锂配合物和铝茂。通过单晶X射线结构分析和核磁共振光谱对其结构进行了表征。铝酸锂配合物2-TMEDA的结构表明，Al原子采用四配位模式，与两个丁二烯基Csp2原子和两个乙基Csp3原子键合。锂阳离子位于铝茂环上方。3a的结构表明固态下为二聚体1-乙基铝茂。扩散有序光谱核磁共振谱表明，3a在C6D6溶剂中也是二聚体。然而，在四氢呋喃（THF）溶液中，二聚体3a解离为1-乙基铝茂-THF加合物。用1.0当量的AlEt2Cl处理时，铝酸锂配合物2转化为3a-THF。还研究了铝酸锂配合物的初步反应化学和合成应用。
