Synthesis and Structural Characteristics of Discrete Organoboron and Organoaluminum Hydrides Incorporating Bulky Eind Groups
Synthesis and Structural Characteristics of Discrete Organoboron and Organoaluminum Hydrides Incorporating Bulky Eind Groups
复制标题
含大体积Eind基团的离散有机硼和有机铝氢化物的合成及结构特征
DOI：
10.1021/acs.organomet.6b00633
复制
发表时间：
2016
期刊：
影响因子：
2.8
通讯作者：
Tsukasa Matsuo
中科院分区：
文献类型：
--
作者：
Takahiro Murosaki;Shohei Kaneda;Ryota Maruhashi;Kazuya Sadamori;Yoshiaki Shoji;Kohei Tamao;Daisuke Hashizume;Naoki Hayakawa;Tsukasa Matsuo
大体积的基于Eind的芳基锂（Eind）Li（Eind = 1，1，3，3，5，5，7，7-八乙基-s-氢化茚并苯-4-基）在Et 2 O中与BF 3·OEt 2反应以形成相应的芳基二氟硼烷（Eind）BF 2（1），沿着有痕量的空间密集的二芳基硼烷（Eind）2BH（2）。1与LiAlH_4在THF中反应，得到相应的三氢硼酸锂[Li（thf）]_2[（Eind）BH_3]_2（3），经Me_3SiCl处理，可转化为乙硼烷（6），（Eind）HB（μ-H）_2BH（Eind）（4）。以（Eind）Li和LiAlH 4为原料，在Et 2 O中合成了三氢铝酸锂[Li（OEt 2）]2[（Eind）AlH 3]2（5）。随后将Me 3SiCl加入到5的甲苯溶液中，生成了二铝烷（6），（Eind）HAl（μ-H）2AlH（Eind）（6），4的重同系物。在Et_2O和甲苯的混合溶剂中，二芳基铝烷（6）6与金属锂反应，通过沿着Al-C键的断裂和重组，生成二芳基铝烷（Eind）_2AlH（7）。用X射线晶体学测定了1、2和7的单体结构和3、4、5和6的二聚体结构。
The bulky Eind-based aryllithium, (Eind)Li (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), reacted with BF3·OEt2in Et2O to form the corresponding aryldifluoroborane (Eind)BF2(1), along with a trace amount of the sterically congested diarylborane, (Eind)2BH (2). The reaction of1with LiAlH4in THF led to the isolation of the corresponding lithium trihydroborate [Li(thf)]2[(Eind)BH3]2(3), which can be transformed into the diborane(6), (Eind)HB(μ-H)2BH(Eind) (4), with treatment with Me3SiCl. The Eind-based lithium trihydroaluminate [Li(OEt2)]2[(Eind)AlH3]2(5) has been synthesized by the reaction of (Eind)Li with LiAlH4in Et2O. The subsequent addition of Me3SiCl to a solution of5in toluene produced the dialumane(6), (Eind)HAl(μ-H)2AlH(Eind) (6), the heavier congener of4. The dialumane(6)6reacted with lithium metal in a mixed solvent of Et2O and toluene to give the diarylalumane, (Eind)2AlH (7), via a disproportionation reaction along with the cleavage and recombination of the Al–C bond. The discrete monomeric structures of1,2, and7and dimeric structures of3,4,5, and6have been determined by X-ray crystallography.