Lithium Aluminate Complexes and Alumoles from 1,4-Dilithio-1,3-Butadienes and AlEt2Cl.
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.
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.
Yongliang
Y
Zhang
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.
Junnian
J
Wei
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.
Wen-Xiong
WX
Zhang
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.
Zhenfeng
Z
Xi